POLYURETHANE FOAM FORMING COMPOSITIONS

专利摘要:
The invention relates to the field of polyol components suitable for forming a polyurethane foam, particularly a two-component polyurethane foam, the resulting foams and the methods for their production. The inventors found gassing hydrohalolefin containing polyol components with better shelf life properties, in particular polyol components comprising a gassing hydrohalolefin blowing agent selected from 1,3,3,3-tetrafluoropropene (HFO 1234ze); 2,3,3,3-tetrafluoroprop-1-ene (HFO 1234yf); 1,2,3,3,3-pentafluoropropene (HFO 1225ye); 1,1,3,3,3-pentafluoropropene (HFO 1225zc); 1,1,2,3,3-pentafluoropropene (HFO 1225yc), or combinations thereof, a nitrogen catalyst and a tin catalyst, wherein the tin catalyst comprises a sulfur atom. The inventors also found that shelf life is further improved when the nitrogen catalyst is at least partially protonated by reaction with an acid, such as an organic acid.
公开号:BE1026148B1
申请号:E20195223
申请日:2019-04-05
公开日:2020-07-28
发明作者:Yvo F H Trimbos；Thomas Duijsters；Peter Geboes；Yvan Boeykens
申请人:Soudal Nv；
IPC主号:

专利说明:

Field of the Invention The invention relates to the field of polyol components suitable for forming a polyurethane foam, in particular a two component polyurethane foam.
The polyol components are particularly suitable for use in low pressure two component polyurethane foam sealants.
The invention further relates to the resulting foams and to the methods for their production.
In particular, the invention relates to such compositions wherein the polyol component comprises a gaseous hydrohalefin blowing agent, a nitrogen catalyst and a tin catalyst, the tin catalyst comprising a sulfur atom.
Background of the Invention It is known that low pressure two component polyurethane foams, such as spray foams, are formed from two component systems, the components commonly referred to as an "A" component and a "B" component, which when mixed polymerize into a polyurethane foam.
The "A" component comprises a diisocyanate or a polyisocyanate and optionally a blowing agent and / or additional additives, and the "B" component generally includes a gassing blowing agent, a catalyst, a polyol and optionally additional additives.
The two components are packaged and stored in separate containers or stored in separate compartments within the same container.
Typically, the "A" component and the "B" component are metered through separate lines to a delivery unit, such as an "impingement mixing" or a "static mixing" spray gun or pouring gun, generally in a volume ratio of about 1: 1. In a system with two separate containers, the two components are kept separate throughout this system until they converge in the mixing section of the dispensing unit, such as a mixing piece or a mixing chamber.
Upon release, the liquid content exits as an effervescent foam that reacts and cross-links to form the cellular polyurethane polymer.
The spray foam industry traditionally considers the isocyanate component as the “A” component and the polyol component as the “B” component.
The “A” and “B” assignments can be reversed in some areas.
Environmental concerns and evolving regulations have resulted in the development of hydrohaloolefin blowing agents that have a low global warming potential (GWP) such as trans-1-fluoro-3,3,3-trifluoroprop-1-ene (also known as trans-1,3 , 3,3-tetrafluoropropene or HFO-1234ze (E) and used in the market under the name Solstice® GBA). HFO-1234ze (E) has an ozone-depleting potential of approximately zero and an atmospheric lifetime of 14 days.
Known polyol components comprising HFO-1234ze (E) suffer from one or more undesirable properties as compared to known polyol components using previous generation blowing agents (such as hydrochlorofluorocarbons (CFC), hydrochlorofluorocarbons (HCFC) and hydrofluorocarbons (HFC)). Such undesirable properties are usually related to a reduced shelf life, i.e., reduced reactivity due to aging resulting in low-quality foams.
This reduced shelf life can be characterized by an increased foam density, increased thermal conductivity of the foam, increased gel time, increased tack-free time,
decreased foam stability, etc. when comparing a foam prepared with a fresh polyol component with a foam prepared with an aged polyol component (e.g., stored for several weeks, optionally at elevated temperatures).
US2016 / 0200890 describes HFO-1234ze (E) two component polyurethane spray foam compositions with increased shelf life comprising aromatic polyester polyols and low concentrations of aliphatic polyether polyols in combination with an amine catalyst and an aliphatic metal salt catalyst.
US9550854 describes HFO-1234ze (E) two component polyurethane pour-in-place foam compositions with increased shelf life comprising sterically hindered amines.
WO2016 / 164671 describes HFO-1234ze (E) two component polyurethane spray foam compositions comprising an unspecified tin catalyst and 2,2'-dimorpholinodoethyl ether and having severe shelf life instability and a foam density (fresh steel) of 2.2 pcf (35.24 kg / m ° ) to have. US2014 / 0339723 describes the use of low boiling point and low vapor pressure blowing agents in polyurethane or polyisocyanurate foams to fill voids (especially window frames).
US2014 / 0171527 describes polyol premix compositions comprising a combination of a liquid hydrohalolefin blowing agent, a polyol, a silicone surfactant and a precipitation resistant metal-based catalyst.
US2018 / 022885 describes phase stable polyol compositions comprising phthalic anhydride based polyester polyols.
It is an object of the invention to provide polyol components which contain a gaseous hydrohalolefin and are suitable for forming polyurethane foam and are particularly suitable for use in low pressure two component polyurethane spray foam kits and which have one or more improved shelf life properties. .
It is a further object of the invention to provide polyol components that contain a gaseous hydrohalolefin and are suitable for forming polyurethane foam and are particularly suitable for use in low pressure two component polyurethane spray foam kits that have one or more improved shelf life properties. and which provides foams with a sufficiently low density and / or low thermal conductivity.
Summary of the Invention The inventors have surprisingly found that one or more of these objects can be achieved by the use of a polyol component in accordance with the invention comprising a particular catalyst or catalyst combination as disclosed herein. The HFO-containing polyol components and foams provided herein have been found to be able to compete with older-generation HFC-containing polyol components and resultant foams with respect to shelf life properties of the polyol composition and density and / or thermal conductivity of the polyol composition. resulting foams.
For the purposes of this disclosure, the term "isocyanate component" is intended to mean a combination of an isocyanate such as diisocyanate or polyisocyanate or a combination thereof and optionally a blowing agent and / or additional additives. This isocyanate component is often referred to as "A" component or as the first component.
For the purposes of this disclosure, the terms isocyanate component, "A" component, and first component are used interchangeably.
For the purposes of this disclosure, the term "polyol component" is intended to mean a combination of a blowing agent, a catalyst, a polyol and optionally additional additives.
The polyol component is often referred to as the "B" component or as the second component.
For the purposes of this disclosure, the terms polyol component, "B" component, and second component are used interchangeably.
Thus, in a first aspect, the invention provides a polyol component suitable for producing a two-component polyurethane foam and particularly suitable for use in a two-component polyurethane foam molding kit.
The polyol component includes a polyol, a gaseous hydrohalolefin blowing agent selected from 1,3,3,3-tetrafluoropropene (HFO 1234ze); 2,3,3,3-tetrafluoroprop-1-ene (HFO 1234yf); 1,2,3,3,3-pentafluoropropene (HFO 1225ye); 1,1,3,3,3-pentafluoropropene (HFO 1225zc); 1,1,2,3,3-pentafluoropropene (HFO 1225yc) or combinations thereof, a nitrogen catalyst and a tin catalyst, wherein the tin catalyst comprises a sulfur atom.
A polyol component in accordance with the invention has been found to have improved shelf-life stability.
It has also been found that the resulting foams have a low density, which results in a reduced consumption of reagents for the same foam volume, making the polyol component in accordance with the invention attractive from a technical, an environmental and an economic standpoint.
In a second aspect, the invention provides a two component polyurethane foaming kit wherein the kit comprises an isocyanate component (the "A" component) comprising a suitable isocyanate and an optional blowing agent; and a polyol component (the "B" component) comprising a polyol, a gaseous hydrohalolefin blowing agent selected from 1,3,3,3-tetrafluoropropene (HFO 1234ze); 2,3,3,3-tetrafluoroprop-1-ene (HFO 1234yf); 1,2,3,3,3-pentafluoropropene (HFO 1225ye); 1,1,3,3,3-pentafluoropropene (HFO 1225zc); 1,1,2,3,3-pentafluoropropene (HFO 1225yc) or combinations thereof, a nitrogen catalyst and a tin catalyst, wherein the tin catalyst comprises a sulfur atom.
In a third aspect, the invention provides a polyurethane foam made by a two component polyurethane foam molding kit, wherein the kit comprises an isocyanate component comprising a suitable isocyanate and an optional blowing agent; and a polyol component comprising a polyol; a gassing hydrohalolefin blowing agent selected from 1,3,3,3-tetrafluoropropene (HFO 1234ze); 2,3,3,3-tetrafluoroprop-1-ene (HFO 1234yf); 1,2,3,3,3-pentafluoropropene (HFO 1225ye); 1,1,3,3,3-pentafluoropropene (HFO 1225z0); 1,1,2,3,3-pentafluoropropene (HFO 1225yc) or combinations thereof; a nitrogen stick catalyst; and a tin catalyst, wherein the tin catalyst comprises a sulfur atom.
In a fourth aspect, the invention provides a process for forming a polyurethane foam comprising: e providing an isocyanate component comprising a suitable isocyanate and optionally a blowing agent;
e providing a polyol component comprising a polyol, a gaseous hydrohalefin blowing agent selected from 1,3,3,3-tetrafluoropropene (HFO 1234ze); 2,3,3,3-tetrafluoroprop-1-ene (HFO 1234yf); 1,2,3,3,3-pentafluoropropene (HFO 1225ye); 1,1,3,3,3-pentafluoropropene (HFO 1225zc); 1,1,2,3,3-pentafluoropropene (HFO 1225yc) or combinations thereof, a nitrogen rod catalyst; and a tin catalyst, wherein the tin catalyst comprises a sulfur atom; and e mixing said isocyanate component and said polyol component.
Thus, the invention provides new polyurethane foam-forming compositions, the resulting foams and methods for their production.
These and other aspects of the invention will become apparent from the following detailed description and the accompanying examples.
It will become apparent to those skilled in the art that during the formation of polyurethane foams, various competing reactions take place, and that by taking suitable measures as known in the art (e.g. varying the ratio of isocyanate groups to alcohol groups during the foaming process and / or using suitable catalysts (e.g., trimerization catalysts)), the polyol component in accordance with the invention can also be used for purposes such as the formation of polyisocyanurates.
Detailed Description of the Invention Reference is made to substances, components, or ingredients existing at the time just before they first came into contact with each other, formed in situ, blended, or mixed with one or more other substances, components. or ingredients in accordance with the current disclosure.
A substance, component or ingredient identified as a composition, reaction product, resulting mixture, or the like may acquire an identity, property, or characteristic through a chemical reaction or transformation during contacting, forming, blending, or mixing in situ when performed in accord with this disclosure through the application of common sense and the usual skills of an average chemist.
The transformation from chemical reactants or starting materials to chemical products or final materials is a continuously evolving process, independent of the speed at which it happens.
Accordingly, when such a transformative process takes place, there may be a mixture of starting and ending materials, as well as intermediates.
Unless otherwise stated, definitions of (relative) amounts of components refer to the composition as it is.
A first aspect of the invention relates to a polyol component suitable for producing two-component polyurethane foams and particularly suitable for use in a two-component polyurethane foam molding kit.
The polyol component includes a polyol; a gaseous hydrohalolefin blowing agent selected from 1,3,3,3-tetrafluoropropene (HFO 1234ze); 2,3,3,3-tetrafluoroprop-1-ene (HFO 1234yf); 1,2,3,3,3-pentafluoropropene (HFO 1225ye); 1,1,3,3,3-pentafluoropropene (HFO 1225zc); 1,1,2,3,3-pentafluoropropene (HFO 1225yc) or combinations thereof; a nitrogen stick catalyst; and a tin catalyst, wherein the tin catalyst comprises a sulfur atom.
The polyol component suitable for use in a two component polyurethane foam molding kit 40 is also interchangeably referred to herein as the "B" component.
In preferred embodiments, the polyol component is suitable for use in a two component polyurethane syringe foaming kit. For the purpose of this document, suitable for use in a syringe foaming kit should be interpreted as meaning that it is possible to obtain a gel time of a foam made with said polyol component of less than 70 seconds, preferably in less than 65 seconds, preferably less than 60 seconds. It has been surprisingly found that the polyol component according to the invention exhibits one or more desirable characteristics such as improved shelf life, low foam density of the foam made with the polyol component according to the invention, low thermal conductivity of the foam made with the polyol component according to with the invention. This improved shelf life can be characterized by a small increase in foam density, a small increase in thermal conductivity of the foam, a small increase in gel time, a small increase in tack-free time, a small decrease in foam stability, etc. after comparing a foam prepared with a fresh polyol component with a foam prepared with an aged polyol component (e.g., stored for several weeks, optionally at elevated temperatures).
In embodiments of the invention, there is provided a polyol component suitable for use in a two component polyurethane foaming kit, comprising a polyol; a gassing hydrohalolefin blowing agent; a nitrogen catalyst; and a tin catalyst, wherein the tin catalyst comprises a sulfur atom and wherein the polyol component has an increased shelf life. As shown in the accompanying examples, and explained in the following paragraphs, various methods have been found suitable to evaluate the shelf life of the polyol component in accordance with the invention.
A preferred method of assessing the shelf life of a polyol component is to determine the catalytic decay ratio (CDR), defined as the ratio of the aged gel time and the initial gel time of the polyurethane foam sprayed with the polyol component in accordance with the invention, after 2 , 7, 14, 21 or 28 days, preferably 7 days of aging at 50 ° C. When determining the CDR, the isocyanate component (the “A” component) has not aged and the spray parameters, such as component ratios, additional additives, mixing method, flow rate, etc. must all be the same.
In embodiments in accordance with the invention, there is provided a polyol component suitable for use in a two component polyurethane foaming kit comprising a polyol; a gassing hydrohalolefin blowing agent; a nitrogen catalyst; and a tin catalyst, wherein the tin catalyst comprises a sulfur atom, the polyol component exhibiting a catalytic decay ratio determined after 7 days, preferably 28 days of aging at 50 ° C, of less than 2, preferably less than 1.6, preferably less than 1.5 , preferably less than 1.4, preferably less than 1.3, preferably less than 1.2.
Another preferred method of evaluating the shelf life of a polyol component is by comparing the initial tack-free time to the aged tack-free time of a polyurethane foam sprayed using the polyol components in accordance with the invention, and determining the rise in tack-free time after 2.7, 14, 21 or 28 days, preferably 7 days of aging 40 at 50 ° C, expressed as "% rise". The isocyanate component (the “A” component ”) has not been aged and the spray parameters such as component ratios, additional additives, mixing method, flow rate, etc. must all be the same.
In embodiments in accordance with the invention, there is provided a polyol component suitable for use in a two component polyurethane foam molding kit comprising a polyol; a gassing hydrohalolefin blowing agent; a nitrogen catalyst; and a tin catalyst, wherein the tin catalyst comprises a sulfur atom, wherein the polyol component shows an increase in tack-free time determined after 7 days, preferably 28 days aging at 50 ° C of less than 50%, preferably less than 30%, preferably less than 20%, preferably less than 15%, preferably less than 10%, preferably less than 5%.
Thus, the invention provides a polyol component suitable for use in a two-component polyurethane foaming sealant comprising a polyol; a gassing hydrohalolefin blowing agent; a nitrogen catalyst; and a tin catalyst, wherein the tin catalyst comprises a sulfur atom, wherein the polyol component is characterized by a CDR determined after 7 days, preferably 28 days of aging at 50 ° C, of less than 2, preferably less than 1.6, preferably less than 1.5, preferably less than 1.4, preferably less than 1.3, preferably less than 1.2 and / or an increase in tack-free time determined after 7 days, preferably 28 days after aging at 50 ° C, of less than 50%, preferably less than 30%, preferably less than 20%, preferably less than 15%, preferably less than 10%, preferably less than 5%.
Polyol The polyol component may comprise a single polyol or multiple polyols often used and sold as a polyol pre-mix. The one or more polyols present in the polyol component can be any polyol known in the art to prepare a polyurethane foam.
As used herein, "polyol" refers to a molecule that has an average number of hydroxyl groups greater than 1.0 hydroxyl group per molecule. As used herein, "polyol pre-mix" refers to the total blend of polyols present in the polyol component, regardless of origin (e.g., added separately to the polyol component or added as a pre-mixed blend of polyols sold as such).
Useful polyols include one or more of a sucrose-containing polyol; phenol, a phenol-formaldehyde-containing polyol; a glucose-containing polyol; a sorbitol-containing polyol; a methyl glucoside-containing polyol; an aromatic polyester polyol; an aliphatic polyester polyol; an aromatic polyether polyol; an aliphatic polyether polyol; a polybutadiene polyol; a polycaprolactone polyol; a polycarbonate polyol; a hydroxyl terminal polyolefin polyol; a graft polyol; glycerol; ethylene glycol; diethylene glycol; propylene glycol-containing polyol; graft copolymers of polyether polyols with a vinyl polymer; a copolymer of a polyether polyol with a polyurea; one or more of (a) condensed with one or more of (b): (a) glycerin, ethylene glycol, diethylene glycol, trimethylol propane, pentaerythritol, soybean oil, lecithin, tall oil, palm oil, castor oil; (b) ethylene oxide, propylene oxide, a mixture of ethylene oxide and propylene oxide; or combinations thereof. Preferred polyols include polyether polyols, polyester polyols, or a mixture thereof.
Examples of polyether polyols include alkylene oxide adducts of active hydrogen compounds such as water, alcohols, phenols and the like. Preferred alkylene oxides are styrene oxide, ethylene oxide, propylene oxide and / or butylene oxide. Examples of alcohols include divalent alcohols such as ethylene glycol and propylene glycol and polyvalent alcohols such as glycerol and sucrose; examples of phenols include hydroquinone, bisphenol A and the like. Examples of polyester polyols include condensed polyester polyols prepared by reacting a polyvalent alcohol (a bivalent or trivalent alcohol or the like as described above) with a polybasic acid (succinic, adipic, sebacic, maleic, dimeric, trimellitic, phthalic, terephthalic or the like) ), polylactone polyols prepared by ring-opening polymerization of a lactone such as an ε-lactone, the alkylene oxide adducts thereof, and the like.
Most preferably, the polyols include aliphatic polyether polyols, aliphatic polyester polyols, aromatic polyester polyols, and combinations thereof. In preferred embodiments, the polyol or polyol premix used in the polyol component comprises a sucrose polyol.
In embodiments, the polyol or polyol premix used in the polyol component contains an excess of polyether and / or polyester polyol, such as greater than 50 wt% based on the total weight of polyol present in the polyol component, greater than 70 wt%, more than 85 wt.%, more than 95 wt.%, more than 98 wt.%, more than 99 wt.%.
In embodiments, the polyol or polyol premix used in the polyol component contains an excess of aromatic polyol, such as greater than 50 wt.% Based on the total weight of polyol present in the polyol component, greater than 70 wt.%, Greater than 85 wt. %, more than 95 wt.%, more than 98 wt.%, more than 99 wt.%.
In other embodiments, the polyol or polyol pre-mix used in the polyol component contains an excess of aliphatic polyol, such as greater than 50 wt.% Based on the total weight of polyol present in the polyol component, greater than 70 wt.%, Greater than 85 wt. .%, more than 95 wt.%, more than 98 wt.%, more than 99 wt.%.
In preferred embodiments, the polyol or polyol premix used in the polyol component comprises a polyol selected from the group consisting of aliphatic polyether polyols, aliphatic polyester polyols, aromatic polyester polyols, and combinations thereof. In embodiments, the polyol or polyol premix used in the polyol component consists of aliphatic polyether polyols, aliphatic polyester polyols, aromatic polyester polyols, and combinations thereof.
The polyols generally have a molecular weight ranging from 200 to 6000 g / mol, more preferably from 250 to 2000 g / mol, and most preferably from 250 to 1000 g / mol. The polyol or at least one polyol of the polyol premix preferably has a hydroxyl number (OH number) ranging from 28 to 800 mg / KOH g. Hydroxyl number refers to the number of reactive hydroxyl groups available and is expressed as the amount of milligrams of potassium hydroxide equivalent to the hydroxyl content of one gram of the polyol steel.
The polyol or at least one polyol of the polyol premix preferably has a number average hydroxyl functionality (Fn) of 9 or less, more preferably 8 or less. The number average of hydroxyl functionality refers to the average number of hydroxyl groups present in a molecule of the polyol and can be calculated as the ratio of the total amount of moles of OH in the polyol or polyol pre-mix to the total amount of moles of polyol.
It has been found that the shelf life of the polyol formulations in accordance with the invention are further improved when the polyol is amine free. Accordingly, in preferred embodiments, the polyol or polyol pre-mix used in the polyol component is free of amines. In embodiments, the polyol or polyol pre-mix used in the polyol component contains less than 5 wt% nitrogen, less than 2 wt%, or less than 1 wt% based on the total weight of polyol present in the polyol component. In embodiments, the nitrogen content of the polyol or polyol pre-mix used in the polyol component does not exceed 0.9, 0.8, 0.7, 0.6, 0.5, 0.4, 0.3, 0.2, 0.1, 0.09, 0.08, 0.07, 0.06 or 0.05 wt.% Based on the weight of the polyol pre-mix, and more preferably a nitrogen content that does not exceed 0.1 wt.% based on the total weight of polyol present in the polyol component. The nitrogen content of the polyol pre-mix can be determined by ASTM D 6979-14.
In embodiments, the polyol or polyol premix is present in the polyol component in an amount of from 20 wt.% To 95 wt.%, Preferably from 30 wt.% To 60 wt.%, And more preferably from 40 wt.% To 50 wt% based on the total weight of the polyol component.
In preferred embodiments, the polyol or polyol pre-mix comprises glycerol.
Blowing Agent In embodiments, the term "gaseous hydrohalolefin blowing agent" refers to a hydrohalolefin blowing agent having a boiling point of less than 18 ° C at 1 atm while the term "liquid hydrohalolefin blowing agent" refers to a hydrohalolefin blowing agent having a boiling point greater than 18 ° C at 1 atm.
When referring to a compound without any stereochemical designation (such as (cis), (trans), (E), (Z)), any stereoisomer of the compound is included. In preferred embodiments, the gaseous hydrohalolefin blowing agent used in the polyol component comprises HFO 1234ze, preferably HFO 1234Ze (E).
The inventors have also found that the polyol component may optionally also contain other blowing agents, preferably a liquid hydrohalolefin blowing agent. The combination of a gaseous hydrohalolefin blowing agent and a liquid hydrohalolefin blowing agent has been found to further improve shelf life stability while still resulting in foams of acceptable density. In embodiments of the invention, the polyol component as provided herein further comprises a liquid hydrohalolefin blowing agent selected from 1,1,1,4,4,4-hexafluoro-2-butene (HFO-1336mzz), 1-chloro-3,3,3 , trifluoropropene (HFO-1233zd) and combinations thereof, preferably HFO-1336mzz (Z), HFO-1233zd (E) and combinations thereof. It should be noted that the abbreviation "HFO" commonly used in the art when referring to liquid hydrohalolefin blowing agents (such as HFO-1233zd) is sometimes replaced by the term "HCFO".
Thus, in preferred embodiments, there is provided a polyol component suitable for producing a two component polyurethane foam comprising a polyol, HFO 1234ze, a nitrogen catalyst and a tin catalyst, wherein the tin catalyst comprises a sulfur atom.
In embodiments in accordance with the invention, the gaseous hydrohalolefin blowing agent is present in the polyol component in an amount of 5-50 wt%; preferably 10-30 wt%, preferably 15-25 wt% based on the total weight of the polyol component.
In embodiments in accordance with the invention, the gaseous hydrohalolefin blowing agent is present in the polyol component in an amount greater than 1 wt.%, Preferably greater than 5 wt.%, Preferably greater than 10 wt.%, Preferably greater than 15 wt. wt% based on the total weight of the polyol component.
In embodiments in accordance with the invention, the gaseous hydrohalolefin blowing agent is present in the polyol component in an amount of less than 70 wt.%, Preferably less than 50 wt.%, Preferably less than 40 wt.%, Preferably less than 30 wt. % based on the total weight of the polyol component.
In embodiments in accordance with the invention, the polyol component also includes a liquid hydrohalolefin blowing agent in an amount of 0.1-30 wt.%, Preferably 0.5-15 wt.% Based on the total weight of the polyol component.
In embodiments in accordance with the invention, the liquid hydrohalolefin blowing agent is present in the polyol component in an amount of more than 0.01 wt.%, Preferably more than 0.05 wt.%, Preferably more than 0.1 wt.%, Preferably more than 1 wt%, preferably more than 5 wt%, based on the total weight of the polyol component.
In embodiments in accordance with the invention, the liquid hydrohalolefin blowing agent is present in the polyol component in an amount of less than 50 wt.%, Preferably less than 30 wt.%, Preferably less than 20 wt.%, Preferably less than 10 wt. wt%, preferably less than 8 wt% based on the total weight of the polyol component.
In more preferred embodiments in accordance with the invention, the polyol component comprises halogenated non-hydrohalolefin blowing agents in an amount of less than 10 wt.%, Preferably less than 5 wt.%, Preferably less than 1 wt.%, Preferably less than 5 wt%, preferably 0 wt% based on the total weight of the polyol component.
Thus, in preferred embodiments in accordance with the invention there is provided a polyol component suitable for use in a two component polyurethane foam molding kit comprising a polyol; a gassing hydrohalolefin blowing agent; a nitrogen catalyst; and a tin catalyst, wherein the tin catalyst comprises a sulfur atom, and wherein the polyol component is substantially free of chlorofluorocarbon and hydrochlorofluorocarbon blowing agents.
In embodiments, the polyol component is additionally free of hydrofluorocarbon blowing agents.
Nitrogen Catalyst The nitrogen catalyst used in the polyol component may be any amine compound, the corresponding ammonium ion, or combinations thereof suitable for catalyzing to form a polyurethane foam.
It is clear to one skilled in the art that a weak base such as an amine is always in equilibrium with its conjugated acid, the ammonium ion.
In contrast, the inventors have found that the shelf life stability of the systems in accordance with the invention is further improved when the nitrogen catalyst is an amine compound suitable for catalyzing to form a polyurethane foam that is at least partially protonated by the amine at least in part. reacting with an acid to generate the corresponding ammonium ion.
In preferred embodiments in accordance with the invention, the nitrogen catalyst is used in the form of an ammonium salt.
In embodiments in accordance with the invention, an organic acid has been used to generate the nitrogen catalyst, preferably an organic polyacid.
In preferred embodiments in accordance with the invention, an organic acid is used to generate the nitrogen catalyst selected from the group consisting of the aliphatic organic carboxylic acids, aliphatic organic dicarboxylic acids, aliphatic organic tricarboxylic acids and combinations thereof, preferably selected from the group consisting of oxalic acid, malonic acid , adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, formic acid, succinic acid, acetic acid, propionic acid, glutaric acid and combinations thereof, more preferably adipic acid, succinic acid, glutaric acid and combinations thereof.
In preferred embodiments in accordance with the invention, the nitrogen catalyst is an ammonium salt resulting from the reaction of an amine selected from the group of 2,2'-dimorpholinodiethyl ether or dicyclohexylmethylamine and combinations thereof with an acid selected from the group of aliphatic organic dicarboxylic acids.
The ammonium ion may be generated in situ or may be generated before the nitrogen catalyst is added to the polyol component.
In preferred embodiments of the invention, the nitrogen catalyst comprises a soluble ammonium salt such as an aliphatic organic dicarboxylic acid ammonium salt, preferably succinic acid ammonium salt.
In more preferred embodiments of the invention, the nitrogen catalyst comprises an ammonium salt resulting from the reaction of an amine selected from the group of 2,2'-dimorpholinodiethyl ether or dicyclohexylmethylamine and combinations thereof with succinic acid.
In embodiments, the nitrogen catalyst contains a quaternary ammonium compound, such as a quaternary ammonium compound of the formula (NR'R2R3R *% * where R1, R2, R3 and R * are each independently selected from the group consisting of alkyl and alkenyl, preferably from the group consisting of methyl, ethyl and propyl, most preferably from the group consisting of methyl and ethyl.
In more preferred embodiments, the quaternary ammonium compound is tetramethylammonium.
In embodiments, the quaternary ammonium compound as described herein is provided in the form of a salt with the conjugate base of an organic acid, preferably an organic polyacid.
In preferred embodiments of the invention, the quaternary ammonium compound as described herein is provided in the form of a salt with the conjugated base of an organic acid selected from the group consisting of aliphatic organic carboxylic acids, aliphatic organic dicarboxylic acids, aliphatic organic tricarboxylic acids and combinations thereof, at preferably selected from the group consisting of oxalic acid, malonic acid, adipic acid, pimelic acid, submeric acid, azelaic acid, sebacic acid, formic acid, succinic acid, acetic acid, propionic acid, glutaric acid and combinations thereof, more preferably adipic acid, succinic acid, glutaric acid and combinations thereof, most preferably succinic acid .
Thus, in more preferred embodiments, the nitrogen catalyst contains tetramethylammonium succinate.
In embodiments in accordance with the invention, the nitrogen catalyst has low nucleophilicity, preferably the nitrogen catalyst is sterically hindered. Suitable sterically hindered amines can contain a sterically hindered primary amine, secondary amine or tertiary amine. Suitable sterically hindered tertiary amines for use as nitrogen catalyst used in the polyol component may include dicyclohexylmethylamine; ethyldiisopropylamine; dimethylcyclohexylamine; dimethylisopropylamine; methylisopropylbenzylamine; methylcyclopentylbenzylamine; isopropyl-sec-butyl-trifluoroethylamine; diethyl- (α-phenylethyhamine, tri-n-propylamine, or combinations thereof Suitable sterically hindered secondary amine catalysts may include dicyclohexylamine, f-butylisopropylamine, di-t-butylamine, cyclohexyl-t-butylamine, di-sec-butylamine, dicyoplylamine; di- (α-trifluoromethylethyhamine; di- (α-phenylethyl) amine; or combinations thereof Suitable sterically hindered primary amine catalysts may contain triphenylmethylamine and 1,1-diethyl-n-propylamine or combinations thereof Other suitable sterically hindered amines may include morpholines , imidazoles, ether-containing compounds, etc. These ether compounds contain dimorpholinodiethyl ether, N-ethylmorpholine, N-methylmorpholine, bis (dimethylaminoethyl) ether imidazole, N-methylimidazole, 1,2-dimethylimidazole, dimorpholinodimethyl ether, N, N, N ', N' , N ", N" -pentamethyldiethylenetriamine, N, N, N ', N', N ", N" "- pentaethyldiethylenetriamine, N, N, N ', N', N", N "-pentamethyldipropylenetriamine, bis (diethy laminoethyl) ether, bis (dimethylaminopropyl) ether. The polyol component suitable for use in a two-component polyurethane foaming kit (the polyol component) may contain two, three, four or more nitrogen catalysts, preferably sterically hindered amine catalysts as described above. In embodiments in accordance with the invention, the nitrogen catalyst is present in the polyol component in an amount of 0.1-10 wt.%, Preferably 0.5-7 wt.%, More preferably
0.5-5 wt.% Based on the total weight of the polyol component. In preferred embodiments in accordance with the invention, the nitrogen catalyst is present in the polyol component in an amount of 0.1-10 wt.%, Preferably 0.5-7 wt.%, More preferably 1-5 wt.% Based on the total weight of the polyol component. In embodiments in accordance with the invention, the nitrogen catalyst is present in the polyol component in an amount of more than 0.01 wt.%, Preferably more than 0.05 wt.%, Preferably more than 0.1 wt.%, Preferably more than 0.5 wt. %, preferably greater than 0.9 wt.% based on the total weight of the polyol component. In embodiments in accordance with the invention, the nitrogen catalyst is present in the polyol component in an amount of less than 20 wt.%, Preferably less than 9 wt.%, Preferably less than 8 wt.%, Preferably less than 7 wt. %, preferably less than 6 wt.% based on the total weight of the polyol component. If the nitrogen catalyst has been added in part or in full or is present as an ammonium salt, the amounts are calculated by taking into account the weight of the ammonium ion (and not the weight of the entire salt). 40 Tin catalyst
The inventors have surprisingly found that when tin catalysts comprising a sulfur atom are used in the polyol component in accordance with the invention, a polyol component with improved shelf life properties is obtained. The tin catalysts comprising a sulfur atom can be any tin catalyst comprising a sulfur atom suitable for catalyzing the formation of a polyurethane foam such as tin catalysts comprising a thiol or its salts and / or derivatives.
In embodiments in accordance with the invention, the tin catalyst comprising a sulfur atom is a tin mercaptide. In preferred embodiments, the tin catalyst does not include carboxylate groups. In highly preferred embodiments, the tin catalyst is a tin mercaptide free of carboxylate groups.
In preferred embodiments in accordance with the invention, the tin catalyst comprising a sulfur atom is selected from the group consisting of: dioctyltin dilauryl mercaptide, dimethyltin bis (2-ethylhexyl thioglycolate), dioctyltin bis (2-ethylhexyl thioglycolate), octyltin tris (2-ethylhexyl) thioglycolate), dibutyltin bis (2-ethylhexyl thioglycolate), dimethyltin di-isooctyl thioglycolate, methyltin triisooctyl thioglycolate, dimethyltindilaury mercaptide, dibutyltin dilauryl mercaptide, and combinations thereof, preferably dibutyltin indilauryl merctyl mercaptide, dimethyltindauryl mercaptide, dimethyltindauryl mercaptide, dimethyltindauryl merctyl merctyl mercaptide, dimethyltindauryl merctyl mercury In embodiments in accordance with the invention, the tin catalyst comprising a sulfur atom is present in the polyol component in an amount of 0.001-10 wt.%, Preferably 0.005-5 wt.%, More preferably 0.01-2 wt.% Tin based on the total weight of the polyol component.
In embodiments in accordance with the invention, for example to provide a polyol component for "pour-in-place" applications, the tin catalyst comprising a sulfur atom is present in the polyol component in an amount of 0.001-5 wt.%, Preferably 0.005- 2.5 wt.%, More preferably 0.01-1 wt.% Tin based on the total weight of the polyol component.
In embodiments in accordance with the invention, for example for sprouting applications, the tin catalyst comprising a sulfur atom is present in the polyol component in an amount of
0.001-5 wt.%, Preferably 0.005-2.5 wt.%, More preferably 0.01-1 wt.% Tin based on the total weight of the polyol component.
In embodiments in accordance with the invention, the tin catalyst comprising a sulfur atom is present in the polyol component in an amount of greater than 0.005 wt.%, Preferably greater than 0.01 wt.%, Preferably greater than 0.05 wt.%, Preferably more than 0.1 wt.%, preferably more than
0.4 wt.% Tin based on the total weight of the polyol component. In embodiments in accordance with the invention, the tin catalyst comprising a sulfur atom is present in the polyol component in an amount of less than 20 wt%, preferably less than 9 wt%, preferably less than 8 wt%, preferably less than 7 wt.%, preferably less than 5 wt.% tin based on the total weight of the polycomponent.
In preferred embodiments, the polyol component in accordance with the invention comprises metal catalysts other than the tin catalyst comprising a sulfur atom as described herein in an amount less than 10 wt.%, Preferably less than 5 wt.%, Preferably less than 1 wt.%, preferably less than 0.1 wt%, preferably about 0 wt%, preferably 0 wt% based on the total weight of the polyol component.
In embodiments, the polyol component in accordance with the invention comprises catalysts other than the nitrogen catalyst and the tin catalyst described herein in an amount less than 10 wt%, preferably less than 5 wt%, preferably less than 1 wt%, preferably less than
0.1 wt%, preferably about 0 wt%, preferably 0 wt% based on the total weight of the polyol component. Thus, in preferred embodiments in accordance with the invention, there is provided a polyol component that does not include catalysts other than the nitrogen catalyst and the tin catalyst. Water is not considered a catalyst and may be present.
It is within the skill of the art to adjust the concentration of tin catalyst and amine to provide a polyol component suitable for pour-in-place applications, or a component suitable for spray applications.
Other Additives The polyol component in accordance with the present invention may include other materials such as, but not limited to, water, flame retardants, colorants, fillers, surfactants, additional catalysts, additional blowing agents, propellants, emulsifiers, solvents and / or plasticizers.
A surfactant can be added to the polyol component to improve characteristics such as foaming, foam cell size control, reduction of disintegration during formation, etc. A foam with small bubbles or cells of uniform size in it is desirable as this will reduce the most desirable physical properties such as compressive strength and thermal conductivity. Thus, in embodiments in accordance with the invention, the polycomponent may include a surfactant.
In embodiments in accordance with the invention, the polycomponent comprises a silicone surfactant. In preferred embodiments, the silicone surfactant comprises a polysiloxane polyoxyalkylene block copolymer. In embodiments, the silicone surfactant is selected from the group consisting of Momentive's L-5130, L-5180, L-5340, L-5440, L-6100, L-6900, L-6980 and L-6988; Air Products DC-193, DC-197, DC-5582, and DC-5598; and B-8404, B-8407, B-8409 and B-8462 from Goldschmidt AG of Essen, Germany. Others are described in U.S. Pat. Nos. 2,834,748; 2,917,480; 2,846, 458 and 4,147,847.
In embodiments in accordance with the invention, the surfactant is present in the polycomponent in an amount of 0.1-10 wt.%, Preferably 0.5-7 wt.%, More preferably 1-5 wt.% Based on the total weight of the polyol component. In embodiments in accordance with the invention, the surfactant is present in the polyol component in an amount greater than
0.01 wt%, preferably more than 0.05 wt%, preferably more than 0.1 wt%, preferably more than 0.5 wt%, preferably more than 0.9 wt% based on the total weight of the polyol component. In embodiments in accordance with the invention, the surfactant is present in the polyol component in an amount of less than 10 wt%, preferably less than 9 wt%, preferably less than 8 wt%, preferably less than 7 wt. %, preferably less than 6 wt.% based on the total weight of the polyol component. Any flame retardant known in the art may be included in the polyol component in accordance with the invention. Examples of suitable flame retardants are tris (2-chloroethyl) phosphate, tris (2-chloropropyl) phosphate, tris (1-chloro-2-propyl) phosphate, tris (2,3-dibromopropyl) phosphate, tris (1,3-dichloropropyl ) phosphate, tri (2-chloroisopropyl) phosphate, tricresyl phosphate, tri (2,2-dichloroisopropyl) phosphate, diethyl | N, N-bis (2-hydroxyethyl) aminomethyl phosphonate, dimethyl methyl phosphonate, tri (2,3-dibromopropyl) phosphate, tri (1,3-dichloropropyl) phosphate, and-tetrakis (2-chloroethyl) ethylenediphosphate, triethyl phosphate, diammonium phosphate, various aromatic compounds, antimony oxide, aluminum trinydrate, polyvinyl chloride, melamine, tribromoneopentyl alcohol, and combinations thereof, preferably tribromoneopentyl alcohol, tris (1-chloro-2-propyl) phosphate, triethyl phosphate and combinations thereof. The flame retardant may be present in the polyol component in accordance with the present invention, for example, in an amount of 1-50 wt.%, 5-40 wt.%, 15-30 wt.% Based on the total weight of the polyol component or in an amount of more than 0.1 wt.%, more than 1 wt.%, more than 10 wt.% based on the total weight of the polyol component. Any colorant known in the art can be included in the polyol component in accordance with the invention. Examples of suitable dyes are titanium dioxide, zinc oxide, iron oxide, antimony oxide, chrome green, chrome yellow, iron bluesienna, molybdate orange and organic pigments such as parred, benzidine yellow, toluidine red, toners and phthalocyanines, preferably a reactive polymer with a chromophore. The dye may be present in the polyol component in accordance with the present invention, for example in an amount of 0.0001-10 wt.%,
0.001-5 wt.%, 0.001-1 wt.%, 0.001-0.5 wt.%, 0.001-0.1 wt.% Based on the total weight of the polyol component or in an amount greater than 0.0001 wt%, more than 0.001 wt.%, more than
0.01 wt.% Based on the total weight of the polyol component. The polyol component in accordance with the invention may be substantially free of dyes and contains the dyes in an amount of less than 0.001 wt.%, Less than 0.0001 wt.%, Less than 0.00001 wt.% Based on the total weight of the polyol component. Any filler known in the art may be included in the polyol component suitable for use in a two-component polyurethane foam molding kit in accordance with the invention. Examples of suitable fillers are aluminum silicate, calcium silicate, magnesium silicate, calcium carbonate, barium sulfate, calcium sulfate, glass fibers, carbon black and silica. The filler may be present in the polyol component suitable for use in a two-component polyurethane foam molding kit comprising a polyol; a gassing hydrohalolefin blowing agent; a nitrogen catalyst; and a tin catalyst; wherein the tin catalyst comprises a sulfur atom 40 in accordance with the present invention, for example in an amount of 0.0001-50wt.%, 0.001-30 wt.%, 0.01-10 wt.%, 0.01-5 wt.%, 0.01-2 wt. % based on the total weight of the polyol component, or in an amount greater than 1 wt.%, greater than 5 wt.%, greater than 10 wt.% based on the total weight of the polyol component. The polyol component suitable for use in a two component polyurethane foam molding kit, comprising a polyol; a gassing hydrohalolefin blowing agent; a nitrogen catalyst, and a tin catalyst, the tin catalyst comprising a sulfur atom in accordance with the present invention may be substantially free of filler and contains the filler in an amount of less than 0.1 wt.%, less than 0.01 wt.%, less than 0.001 wt%, less than 0.0001 wt% based on the total weight of the polyol component.
Any additional blowing agent known in the art can be included in the polyol component in accordance with the invention. Examples of suitable blowing agents are dimethoxymethane, methyl formate, water, propanes, dimethyl ether, butanes, pentanes, liquid hydrohalolefins, preferably the additional blowing agent is a liquid hydrohalolefin blowing agent, as explained in detail above. It is preferred that no chlorofluorocarbons or hydrochlorofluorocarbons blowing agents are included in the polyol component in accordance with the invention. In embodiments, it is additionally preferred that no hydrofluorocarbon blowing agents are included herein. The additional blowing agents may be present in the polyol component according to the invention, for example in an amount of 0.0001-25 wt.%, 0.001-20 wt.%, 0.01-10 wt.%, 0.01-5 wt.% Based on the total weight of the polyol component or in an amount greater than 0.1 wt.%, greater than 1 wt.%, greater than 2 wt.% based on the total weight of the polyol component. The polyol component in accordance with the invention may be substantially free of additional blowing agents and contains additional blowing agents in an amount of less than 0.1 wt.%, Less than 0.01 wt.%, Less
0.001 wt.%, Less than 0.0001 wt.% Based on the total weight of the polyol component. As previously stated herein, it is preferred that the polyol component in accordance with the invention be free of chlorofluorocarbon or hydrochlorofluorocarbon blowing agents. In embodiments, the polyol component is additionally free of hydrofluorocarbon blowing agents. Water may be present in the polyol component according to the invention, for example in an amount of 0.0001-15 wt.%, 0.001-10 wt.%, 0.01-7 wt.%, 0.01-5 wt.%, 0.01-2 wt. % based on the total weight of the polyol component or in an amount greater than 0.1 wt.%, greater than 1 wt.%, greater than 2 wt.% based on the total weight of the polyol component. The polyol component in accordance with the invention may be substantially anhydrous and contain water in an amount of less than 0.1 wt.%, Less than 0.01 wt.%, Less than 0.001 wt.%, Less than
0.0001 wt% based on the total weight of the polyol component.
In preferred embodiments, there is provided a polyol component suitable for use in a two component polyurethane foam molding kit comprising a polyol; HFO 1234ze (E); a nitrogen catalyst; and a tin catalyst, wherein the tin catalyst comprises a sulfur atom.
In preferred embodiments, there is provided a polyol component suitable for use in a two component polyurethane foaming kit, comprising an aliphatic polyether polyol, an aliphatic polyester polyol, an aromatic polyester polyol, and combinations thereof; a gaseous hydrohalolefin blowing agent; a nitrogen catalyst; and a tin catalyst, wherein the tin catalyst comprises a sulfur atom.
In preferred embodiments, there is provided a polyol component suitable for use in a two component polyurethane foam molding kit comprising a polyol; a gassing hydrohalolefin blowing agent; a sterically hindered amine, the corresponding ammonium ion, or combinations thereof; and a tin catalyst, wherein the tin catalyst comprises a sulfur atom.
In preferred embodiments, there is provided a polyol component suitable for use in a two component polyurethane foam molding kit comprising a polyol; a gassing hydrohalolefin blowing agent; a quaternary ammonium compound of the formula (NR'R R * R #) * wherein R ', R2, R3 and R are each independently selected from the group consisting of alkyl and alkenyl, preferably from the group consisting of methyl, ethyl and propyl, most preferably from the group consisting of methyl and ethyl; and a tin catalyst, wherein the tin catalyst comprises a sulfur atom. In preferred embodiments, there is provided a polyol component suitable for use in a two component polyurethane foam molding kit comprising a polyol; a gaseous hydrohalo fin drive gas; a nitrogen catalyst; and a tin mercaptide.
In preferred embodiments, there is provided a polyol component suitable for use in a two component polyurethane foam molding kit, comprising an aliphatic polyether polyol, an aliphatic polyester polyol, an aromatic polyester polyol, and combinations thereof; a gaseous hydrohalo fin drive gas; a nitrogen catalyst; and a tin mercaptide.
In preferred embodiments, there is provided a polyol component suitable for use in a two component polyurethane foam molding kit, comprising an aliphatic polyether polyol, an aliphatic polyester polyol, an aromatic polyester polyol, and combinations thereof; HFO 1234Ze (E); a nitrogen catalyst; and a tin mercaptide.
In preferred embodiments, there is provided a polyol component suitable for use in a two component polyurethane foam molding kit, comprising an aliphatic polyether polyol, an aliphatic polyester polyol, an aromatic polyester polyol, and combinations thereof; HFO 1234Ze (E); a sterically hindered amine, the corresponding ammonium ion, or combinations thereof; and a tin mercaptide.
In preferred embodiments, there is provided a polyol component suitable for use in a two component polyurethane foam molding kit, comprising an aliphatic polyether polyol, an aliphatic polyester polyol, an aromatic polyester polyol, and combinations thereof; HFO 1234Ze (E); a quaternary ammonium compound of the formula (NR'R2R3R *) * wherein R ', R2, R ° and R * are each independently selected from the group consisting of alkyl and alkenyl, preferably from the group consisting of methyl, ethyl and propyl , most preferably from the group consisting of methyl and ethyl; and a tin mercaptide. In preferred embodiments, there is provided a polyol component suitable for use in a two component polyurethane foam molding kit, comprising an aliphatic polyether polyol, an aliphatic polyester polyol, an aromatic polyester polyol, and combinations thereof; HFO 1234ze (E), 2,2'-dimorpholinodiethyl ether, dicyclohexylmethylamine, or combinations thereof; and a tin mercaptide.
In preferred embodiments, there is provided a polyol component suitable for use in a two component polyurethane foam molding kit, comprising an aliphatic polyether polyol, an aliphatic polyester polyol, an aromatic polyester polyol, and combinations thereof; HFO 1234Ze (E); 2,2'-dimorpholinodiethyl ether, dicyclohexylmethylamine, tetramethylammonium, or combinations thereof; and a tin mercaptide.
In preferred embodiments, there is provided a polyol component suitable for use in a two component polyurethane foam molding kit, comprising an aliphatic polyether polyol, an aliphatic polyester polyol, an aromatic polyester polyol, and combinations thereof; HFO 1234Ze (E); tetramethylammonium; and a tin mercaptide.
In preferred embodiments, there is provided a polyol component suitable for use in a two component polyurethane foam molding kit, comprising an aliphatic polyether polyol, an aliphatic polyester polyol, an aromatic polyester polyol, and combinations thereof; HFO 1234Ze (E); 2,2'-dimorpholinodiethyl ether, dicyclohexylmethylamine, or combinations thereof; and dibutyltin dilauryl mercaptide, dimethyltin dilauryl mercaptide, dioctyl dilauryl mercaptide, or combinations thereof.
In preferred embodiments, there is provided a polyol component suitable for use in a two component polyurethane foam molding kit, comprising an aliphatic polyether polyol, an aliphatic polyester polyol, an aromatic polyester polyol, and combinations thereof; HFO 1234Ze (E); 2,2'-dimorpholinodiethyl ether, dicyclohexylmethylamine, tetramethylammonium, or combinations thereof; and dibutyltin dilauryl mercaptide, dimethyltin dilauryl mercaptide, dioctyl dilauryl mercaptide, or combinations thereof.
In preferred embodiments, there is provided a polyol component suitable for use in a two component polyurethane foam molding kit, comprising an aliphatic polyether polyol, an aliphatic polyester polyol, an aromatic polyester polyol, and combinations thereof; HFO 1234Ze (E); dicyclohexylmethylamine; and dibutyltin dilauryl mercaptide, dimethyltin dilauryl mercaptide, dioctyl dilauryl mercaptide, or combinations thereof.
In preferred embodiments, there is provided a polyol component suitable for use in a two component polyurethane foam molding kit, comprising an aliphatic polyether polyol, an aliphatic polyester polyol, an aromatic polyester polyol, and combinations thereof; HFO 1234Ze (E); 2,2'-dimorpholino diethyl ether; and dibutyltin dilauryl mercaptide, dimethyltin dilauryl mercaptide, dioctyl dilauryl mercaptide, or combinations thereof.
In preferred embodiments, there is provided a polyol component suitable for use in a two component polyurethane foam molding kit, comprising an aliphatic polyether polyol, an aliphatic polyester polyol, an aromatic polyester polyol, and combinations thereof; HFO 1234ze (E); tetramethylammonium; and dibutyltin dilauryl mercaptide, dimethyltin dilauryl mercaptide, dioctyl dilauryl mercaptide, or combinations thereof.
In preferred embodiments, there is provided a polyol component suitable for use in a two component polyurethane foam molding kit, comprising from 20 wt.% To 95 wt.%, Preferably from 30 wt.% To 60 wt.%, And more preferably from 40 wt. % 40 to 50 wt% polyol based on the total weight of the polyol component;
e 5-50 wt%, preferably 10-30 wt%, preferably 15-25 wt% gaseous hydrohalolefin blowing agent selected from 1,3,3,3-tetrafluoropropene (HFO 1234ze); 2,3,3,3-tetrafluoroprop-1-ene (HFO 1234yf); 1,2,3,3,3-pentafluoropropene (HFO 1225ye); 1,1,3,3,3-pentafluoropropene (HFO 1225zc); 1,1,2,3,3-pentafluoropropene (HFO 1225yc) or combinations thereof, based on the total weight of the polyol component; e 0.1-10 wt.%, preferably 0.5-7 wt.%, preferably 0.5-5 wt.% nitrogen catalyst based on the total weight of the polyol component; and; e dibutyltin dilauryl mercaptide, dimethyltin dilauryl mercaptide, dioctyl dilauryl mercaptide or combinations thereof in an amount of 0.0001-10 wt.%, preferably 0.005-5 wt.%, more preferably 0.01-2 wt.% of tin based on the total weight of the polyol component . In preferred embodiments, there is provided a polyol component suitable for use in a two component polyurethane foam molding kit, comprising from 20 wt.% To 95 wt.%, Preferably from 30 wt.% To 60 wt.%, And more preferably from 40 wt. % to 50 wt% of an aliphatic polyether polyol, an aliphatic polyester polyol, an aromatic polyester polyol, and combinations thereof based on the total weight of the polyol component; e 5-50 wt.%, preferably 10-30 wt.%, preferably 15-25 wt.% HFO 1234ze (E) based on the total weight of the polyol component; e 0.1-10 wt%, preferably 0.5-7 wt%, preferably 1-5 wt% 2,2'-dimorpholinodiethyl ether, dicyclohexylmethylamine or combinations thereof based on the total weight of the polyol component; and; a tin catalyst comprising a sulfur atom in an amount of 0.0001-10 wt.%, preferably from 0.005-5 wt.%, more preferably 0.01-2 wt.% of tin based on the total weight of the polyol component. In preferred embodiments, there is provided a polyol component suitable for use in a two component polyurethane foam molding kit, comprising from 20 wt.% To 95 wt.%, Preferably from 30 wt.% To 60 wt.%, And more preferably from 40 wt. % to 50 wt% of an aliphatic polyether polyol, an aliphatic polyester polyol, an aromatic polyester polyol, and combinations thereof based on the total weight of the polyol component; 5-50 wt.%, preferably 10-30 wt.%, preferably 15-25 wt.% HFO 1234ze (E) based on the total weight of the polyol component; e 0.1-10 wt.%, preferably 0.5-7 wt.%, preferably 0.5-5 wt.% 2,2'-dimorpholinodiethyl ether, dicyclohexylmethylamine, tetramethylammonium or combinations thereof based on the total weight of the polyol component; and; e a tin catalyst comprising a sulfur atom in an amount of 0.0001-10 wt.%, preferably from 0.005-5 wt.%, more preferably 0.01-2 wt.% of tin based on the total weight of the polyol component.
In preferred embodiments, there is provided a polyol component suitable for use in a two-component polyurethane foam molding kit comprising 20 wt.% To 95 wt.%, Preferably from 30 wt.% To 60 wt.%, And more preferably from 40 wt. % to 50 wt% of an aliphatic polyether polyol, an aliphatic polyester polyol, an aromatic polyester polyol, and combinations thereof based on the total weight of the polyol component; 5-50 wt.%, preferably 10-30 wt.%, preferably 15-25 wt.% HFO 1234ze (E) based on the total weight of the polyol component; e 0.1-10 wt.%, preferably 0.5-7 wt.%, preferably 1-5 wt.% 2,2'-dimorpholinodiethyl ether, based on the total weight of the polyol component; and; e a tin catalyst comprising a sulfur atom in an amount of 0.0001-10 wt.%, preferably from 0.005-5 wt.%, more preferably 0.01-2 wt.% of tin based on the total weight of the polyol component.
In preferred embodiments, there is provided a polyol component suitable for use in a two component polyurethane foam molding kit, comprising from 20 wt.% To 95 wt.%, Preferably from 30 wt.% To 60 wt.%, And more preferably from 40 wt. % to 50 wt% of an aliphatic polyether polyol, an aliphatic polyester polyol, an aromatic polyester polyol, and combinations thereof based on the total weight of the polyol component; e 5-50 wt%, preferably 10-30 wt%, preferably 15-25 wt% HFO 1234ze (E) based on the total weight of the polyol component; e 0.1-10 wt.%, preferably 0.5-7 wt.%, preferably 1-5 wt.% dicyclohexylmethylamine based on the total weight of the polyol component; and; e a tin catalyst comprising a sulfur atom in an amount of 0.0001-10 wt.%, preferably from 0.005-5 wt.%, more preferably 0.01-2 wt.% of tin based on the total weight of the polyol component.
In preferred embodiments, there is provided a polyol component suitable for use in a two component polyurethane foam molding kit, comprising from 20 wt.% To 95 wt.%, Preferably from 30 wt.% To 60 wt.%, And more preferably from 40 wt. % to 50 wt% of an aliphatic polyether polyol, an aliphatic polyester polyol, an aromatic polyester polyol, and combinations thereof based on the total weight of the polyol component; 5-50 wt.%, preferably 10-30 wt.%, preferably 15-25 wt.% HFO 1234ze (E) based on the total weight of the polyol component; e 0.1-10 wt.%, preferably 0.5-7 wt.%, preferably 0.5-5 wt.% tetramethylammonium based on the total weight of the polyol component; and; e a tin catalyst comprising a sulfur atom in an amount of 0.0001-10 wt.%, preferably from 0.005-5 wt.%, more preferably 0.01-2 wt.% of tin based on the total weight of the polyol component.
A second aspect of the invention is a two component polyurethane foaming kit wherein the kit comprises an isocyanate component (the "A" or first component) comprising a suitable isocyanate and an optional blowing agent; and a polyol component (the "B" component or second component) comprising a polyol, a gaseous hydrohalefin blowing agent, a nitrogen catalyst and a tin catalyst, wherein the tin catalyst comprises a sulfur atom. The second component is the polyol component suitable for producing a two component polyurethane foam as described above. In preferred embodiments, the kit is a two component polyurethane spray foam forming kit. It has been found that the polyol component in accordance with the invention previously described herein can be advantageously combined with a variety of isocyanate components to provide a kit that can be conveniently used to produce polyurethane foams. . The kit may be presented in the form of individual cans or containers, for example a polyisocyanate container containing the polyisocyanate component and a polyol container containing the polyol component. The two components may also be presented in the form of a single container in which the two components are stored in different internal compartments. The containers or cans are typically pressurized cylinders or cans equipped with metering valves, as is known in the art. This type of presentation of two component polyurethane spray foam molding kit is known in the art in several variations. In embodiments in accordance with the invention, the pressurized cylinders or cans are partially pressurized by means of nitrogen gas to facilitate release of all stored product from the can. Preferably, the can uses a pressure of at least 5 bar, at least 7 bar, at least 15 bar.
The kit may include a dispensing unit such as a spray gun for dispensing the two components. The dispensing unit may optionally be equipped with a mixer, eg an “impingement” or static mixer.
The two-component polyurethane foaming kit in accordance with the invention may comprise the isocyanate component and polyol component in amounts corresponding to commonly used stoichiometric ratios for foaming. Thus, in embodiments there is provided a two component polyurethane spray foam forming kit in accordance with the invention wherein the kit comprises relative amounts of suitable polyisocyanate or polyol such that the NCO / OH stoichiometric ratio is in a range of 0.9 to 5.0, preferably from
1.0 to 3.0, more preferably from 1.1 to 2.5.
The suitable isocyanate included in the polyisocyanate component may be any polyisocyanate or combinations thereof suitable for use in the formation of a polyurethane foam. As used herein, the term "polyisocyanate" represents any compound having 2 or more isocyanate groups. Any organic polyisocyanate can be used in polyurethane foam synthesis including aliphatic and aromatic polyisocyanates. Suitable organic polyisocyants include aliphatic, cycloaliphatic, araliphatic, aromatic, and heterocyclic isocyanates well known in the field of polyurethane chemistry. In embodiments in accordance with the invention, the suitable isocyanate included in the "A" component is an organic polyisocyanate, for example a compound selected from the group formed by the aromatic diisocyanates (such as 2,4-toluene diisocyanate, 2,6 toluene diisocyanate, mixtures of 2,4- and 2,6-toluene diisocyanates, crude toluene diisocyanate, methylenediphenyl diisocyanate, crude methylenediphenyl diisocyanate and the like); the aromatic triisocyanates (such as 4,4'4 "triphenylmethane triisocyanates, 2,4,6-toluene triisocyanates) the aromatic tetraisocyanates (such as 4,4'-dimethyldiphenylmethane-2,2 ', 5,5'-tetraisocyanate); arylalkyl polyisocyanates (such as xylylene diisocyanate); aliphatic polyisocyanates (such as hexamethylene 1,6-diisocyanate, lysine diisocyanate methyl ester); polymethylene polyphenyl isocyanates; hydrogenated methylenediphenyl isocyanate; m-phenylene di-isocyanate phenylene di-isocyanate; 1,5-phenylene di-isocyanate -2,4-diisocyanate, 4,4-biphenylenedi-isocyanate, 3,3 "dimethoxy-4,4'-biphenyl diisocyanate; 3,3'-dimethyl-4,4'-biphenyl diisocyanate; 3,3 "-Dimethyldiphenylmethane-4,4'-diisocyanate; alkylene diisocyanates (such as trimethylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-methylenebisomatic (cyclohexyl isocyanate)) polyisocyanates (such as m-, and p-phenylene diisocyanate, polymethylene polyphenyl isocyanate, 2,4- and 2,6-toluene diisocyanate, dianisidine diisocyanate, bitoylene isocyanate, naphthylene 1,4-diisocyanate, bis (4-isocyanatophenyl methane, bis (2-methyl-4-isocyanatophenyl) methane), and combinations thereof In preferred embodiments in accordance with the invention, the suitable isocyanate included in the isocyanate component is an aromatic polyisocyanate, such as polymeric methyl diphenyl dioscyanate.
The isocyanate component of the two component polyurethane foam molding kit in accordance with the invention may be provided without blowing agent. Alternatively, the isocyanate component of the two component polyurethane foaming sealant in accordance with the invention may be provided with a blowing agent. In preferred embodiments, the isocyanate component of the two component polyurethane foam molding sealant in accordance with the invention is provided with a blowing agent. The optional blowing agent included in the isocyanate component may be any blowing agent suitable for use in polyurethane foam formation. In preferred embodiments, the optional blowing agent is included in the cyanate component HFO 1234ze, preferably HFO 1234ze (E).
In more preferred embodiments in accordance with the invention, the isocyanate component comprises halogenated non-hydrohalolefin blowing agents in an amount less than 10 wt%, preferably less than 5 wt%, preferably less than 1 wt%, preferably about about 0%, preferably 0 wt.%. based on the total weight of the isocyanate component.
In preferred embodiments in accordance with the invention, there is provided a two-component polyurethane foaming kit, wherein the kit includes a component comprising a suitable isocyanate and an optional blowing agent; and a second component comprising a polyol, a gassing hydrohalolefin blowing agent; a nitrogen catalyst; and a tin catalyst, wherein the tin catalyst comprises a sulfur atom, wherein the isocyanate and the polyol component are substantially free of chlorofluorocarbon and hydrochlorofluorocarbon blowing agents. In embodiments, the kit is also free of hydrofluorocarbon blowing agents.
It will be understood by those of skill in the art that when the polyol component provided by the invention is included in a two component polyurethane foam molding kit, as previously explained herein, the shelf life characteristics may be evaluated on the kit as a whole.
The invention thus provides a two component polyurethane foam molding kit as previously described herein with improved shelf life. Shelf life may be evaluated in accordance with the methods previously described herein for the polyol component, except that the isocyanate component is also aged.
This may be practical, for example, for the embodiments of the kit according to the invention in which the polyol component and the isocyanate component are packaged in a single container with an internal partition for separating the isocyanate component and the polyol component.
A preferred method of evaluating the shelf life of a two component polyurethane foam molding kit is by determining the catalytic decay ratio (CDR), defined as the ratio of the aged gel and the initial gel time of the polyurethane foam sprayed using the kit, after 4 weeks. preferably 8 weeks of aging at 23 ° C.
In determining the CDR, the isocyanate component (the “A” component) is also out of date and the spray parameters such as component ratios, additional additives, mixing method, flow rate, etc. must all be the same.
In embodiments in accordance with the invention, a two component polyurethane foaming kit as described herein is provided wherein the kit exhibits a catalytic decay ratio determined after 8 weeks aging at 23 ° C of less than 2, preferably less than 1.6, preferably less than 1.5, at preferably less than 1.4, preferably less than 1.3, preferably less than 1.2. Another preferred method of evaluating the shelf life of a two component polyurethane foam molding sealant as previously described herein is by comparing the initial tack free time with the aged tack free time and determining the rise in tack free time after 4 weeks, preferably 8 weeks of aging at 23 °. C, expressed as “% increase”. The isocyanate component (the “A” component ”) is also out of date and the spray parameters, such as component ratios, additional additives, mixing method, flow rate, etc must all be the same.
In embodiments in accordance with the invention, a two component polyurethane foam molding kit as previously described herein is provided wherein the kit exhibits an increase in tack-free time determined after 8 weeks aging at 50 ° C of less than 50%, preferably less than 30%, preferably less than 20%, preferably less than 15%, preferably less than 10%, preferably less than 5%. Thus, the invention provides a two component polyurethane foam molding kit as previously described herein wherein the kit is characterized by a CDR determined after 8 weeks of aging at 23 ° C, optionally under pressure as previously described of less than 2, preferably less than 1.6, preferably less than 1.5, preferably less than 1.4, preferably less than 1.3, preferably less than 1.2 and / or an increase in tack-free time determined after 8 weeks of aging at 23 ° C of less than 50%, preferably less than 30% , preferably less than 30%, preferably less than 20%, preferably less than 15%, preferably less than 10%, preferably less than 5%. In a third aspect, the invention provides a foam, preferably a polyurethane foam made from a polyol component wherein the polyol component comprises a polyol; a gassing hydrohalolefin blowing agent; a nitrogen stick catalyst; and a tin catalyst, wherein the tin catalyst comprises a sulfur atom. The polyol component has been described in various embodiments above. In preferred embodiments, the foam is a spray foam.
It has been found that the polyol component in accordance with the invention, previously described herein, can be advantageously used to produce a foam, preferably a polyurethane foam. The foam, preferably polyurethane foam in accordance with the invention may be rigid, flexible or semi-rigid. The foam, preferably polyurethane foam, according to the invention may have a closed cell structure, an open cell structure or mixture of open and closed cells. These foams are used in a variety of well-known applications, including but not limited to thermal insulation, cushioning, propellants, packaging, adhesives, padding, crafts, and decorative and shock absorption. In more preferred embodiments, the foam is a closed cell foam.
The use of a polyol component in accordance with the invention has been found to provide a foam, preferably a polyurethane foam, with excellent thermal insulation characteristics. Thus, in embodiments in accordance with the invention there is provided a foam, preferably a polyurethane foam made with a polyol component in accordance with the invention, wherein the foam has a thermal conductivity of less than 25 mW / m K, less than 24 mW / m K , less than 23 mW / m K, less than 22 mW / m K, less than
21.5 mW / m K, less than 21 mW / m K, measured at an average reference temperature of 10 ° C. A preferred method for measuring thermal conductivity is according to EN 12667.
The use of a polyol component in accordance with the invention has been found to provide a foam, preferably a polyurethane foam, with desirable tightness characteristics. Thus, in embodiments in accordance with the invention there is provided a foam, preferably a polyurethane foam made with a polyol component in accordance with the invention, the foam having a free-rise core density of less than 35 kg / m3, less than 34 kg. / m®, less than 32 kg / m °, less than 31 kg / m °, less than 30 kg / m , less than 29 kg / m °, less than 28 kg / m has. A preferred method for measuring density is according to EN 1602.
In preferred embodiments, the invention provides a closed cell foam, preferably a polyurethane foam comprising a gassing hydrohalolefin in the cells of the foam, the foam, preferably polyurethane foam, having a density of less than 35 kg / m3, less than 34 kg / m3, less than 32 kg / m °, less than 31 kg / m3, less than 30 kg / m , less than 29 kg / m has. In preferred embodiments, the invention provides a closed cell foam, preferably a polyurethane foam made with a polyol component of the invention, wherein the foam, preferably polyurethane foam, has a maximum compressive strength of more than 100 kPa, more than 130 kPa, more than 140 kPa or more than 145 kPa, determined in accordance with EN 826 (2013) In embodiments of the invention, the gassing hydrohalolefin blowing agent in the cells of the foam, preferably polyurethane foam, may be selected from 1,3,3,3-tetrafluoropropene (HFO 1234ze); 2,3,3,3-tetrafluoroprop-1-ene (HFO 1234yf); 1,2,3,3,3-pentafluoropropene (HFO 1225ye); 1,1,3,3,3-pentafluoropropene (HFO 1225zc); 1,1,2,3,3-Pentafluoropropene (HFO 1225yc) or combinations thereof.
In preferred embodiments, the gassing hydrohalolefin blowing agent in the cells of the foam, preferably polyurethane foam comprises HFO 1234ze, preferably HFO 1234ze (E). In preferred embodiments, the gassing hydrohalolefin blowing agent in the cells of the foam, preferably polyurethane foam, is HFO 1234ze, preferably HFO 1234ze (E).
In embodiments in accordance with the invention, the cells of the foam comprise halogenated non-hydrohalolefin blowing agents in an amount of less than 10 wt.%, Preferably less than 5 wt.%, Preferably less than 1 wt.%, Preferably around 0. wt%, preferably 0 wt% based on the total weight of the foam. In embodiments in accordance with the invention, the closed cell gas composition of the foam comprises non-hydrohalolefin blowing agents in an amount of less than 10 wt.%, Preferably less than 5 wt.%, Preferably less than 1 wt. %, preferably around 0 wt%, preferably 0 wt% based on the total weight of the foam. In preferred embodiments in accordance with the invention, there is provided a foam, preferably polyurethane foam comprising a gassing hydrohalolefin in the cells of the foam, wherein the foam, preferably polyurethane foam, is substantially free of chlorofluorocarbon and hydrochlorofluorocarbon blowing agents. In embodiments, the foam is also free of hydrofluorocarbon blowing agents.
A preferred method for determining that the closed cell gas of the foam is free of non-hydrohalolefin blowing agents is by trace analysis of the gas released from the foam, preferably by gas chromatography, preferably coupled to mass spectrometry. A suitable method is the method described in Vollrath, A., Hohl, C. & Seiler, H.G. Fresenius J Anal Chem (1995) 351: 251. This method can be used to determine whether the foam is free from CFCs or HCFCs blowing agents and can be adapted, within the skill of the ordinarily skilled artisan, to determine that the foam is additionally free. is from HFC's blowing agents. Another suitable method is described in A. Reizian, S. Rault, Y. Dat, M. Robba, A mass spectrometric method for the detection of various fluorocarbon derivatives in synthetic flexible and rigid foams (Chemosphere, Volume 27, Issue 9, 1993 , Pages 1681-1690). The composition is preferably determined using a fresh foam sample. In preferred embodiments in accordance with the invention, a polyurethane foam is provided comprising a gassing hydrohalefin in the cells of the foam, wherein the foam, preferably polyurethane foam, is substantially free of chlorofluorocarbon and hydrochlorofluorocarbon and hydrofluorocarbon blowing agents. In a fourth aspect, the invention provides a process for forming a foam, preferably polyurethane foam, comprising: e providing an isocyanate component comprising a suitable isocyanate and optionally a blowing agent; e providing a polyol component comprising a polyol, a gaseous hydrohalolefin blowing agent selected from 1,3,3,3-tetrafluoropropene (HFO 1234ze); 2,3,3,3-tetrafluoroprop-1-ene (HFO 1234yf); 1,2,3,3,3-pentafluoropropene (HFO 1225ye); 1,1,3,3,3-pentafluoropropene (HFO 1225zc); 1,1,2,3,3-pentafluoropropene (HFO 1225yc) or combinations thereof, a nitrogen rod catalyst, and a tin catalyst, the tin catalyst comprising a sulfur atom; and mixing said isocyanate component and said polyol component.
In embodiments in accordance with the invention, the process comprises mixing the "A" component and the "B" component in relative amounts resulting in an NCO / OH stoichiometric ratio in a range of 0.9 to 5.0, preferably 1.0 to 3.0. , more preferably from 1.1 to 2.5. Mixing may include any form of mixing known in the art.
Preferred methods for mixing the “A” component and the “B” component include “impingement” mixing or static mixing.
In preferred embodiments, there is provided a process for forming a spray foam, preferably polyurethane spray foam, comprising: e providing an isocyanate component comprising a suitable isocyanate and optionally a blowing agent; e providing a polyol component comprising a polyol, a gaseous hydrohalolefin blowing agent selected from 1,3,3,3-tetrafluoropropene (HFO 1234ze); 2,3,3,3-tetrafluoroprop-1-ene (HFO 1234yf); 1,2,3,3,3-pentafluoropropene (HFO 1225ye); 1,1,3,3,3-pentafluoropropene (HFO 1225zc); 1,1,2,3,3-pentafluoropropene (HFO 1225yc) or combinations thereof, a nitrogen rod catalyst, and a tin catalyst, wherein the tin catalyst comprises a sulfur atom; and e mixing said isocyanate component and said polyol component to obtain a mixture of the isocyanate component and the polyol component; and e spraying the mixture of the isocyanate component and the polyol component obtained in the previous step. Thus, the invention has been described by reference to certain embodiments discussed above. It will be understood that these embodiments are susceptible to various modifications and alternative forms known to those of skill in the art. Many modifications in addition to the modifications described above can be made to the structures and techniques described herein without departing from the spirit and scope of the invention. Accordingly, while specific embodiments have been described, they are examples only and do not limit the scope of the invention. Furthermore, for an understanding of this document and its claims, it should be understood that the verb "include" and its conjugations are used in a non-limiting sense to indicate that items following the word are included but items not specifically mentioned. are not excluded. Furthermore, the reference to an element by the indefinite article "a" does not preclude the possibility that more than one element is present, unless the context clearly requires that there be only one element. Thus the indefinite article "a" usually means "at least one". The following examples are offered for illustrative purposes only, and are not intended to limit the scope of the present invention in any way. Examples List of abbreviations / connections referenced in the examples:
Abbreviations / Other names Supplier Role of compounds PA240 Isoexter® 4354, Aromatic PA based polyester COIM Polyol polyol TCPP Tris (1-chloro-2-propyl) phosphate ICL-IP Plasticizer, flame retardant DC193 DIMETHYLSILOXANE, ETHYLENE OXIDE BLOCK Evonik Surfactant / COPOLYMER Z40025 foam -4G, sucrose / glycerol propoxylated polyol, Alcupol® Ottchim Polyol R-4110 TEP Triethylphosphate ICL-IP plasticizer DMTDLM dimethyltin dilauryImercaptide, Fomrez® UL-22 Galat Metal catalyst Chemicals glycerine Glycerol Brenntag polyol Struksilether modified polysilicon® Seydether poly siloxylon® 8026 Seydether poly siloxylon® 8026 Seydether poly siloxylactane® 8026 Seydaciller structoxylactane® agent Koc Caproic acid, 2-ethyl, potassium salt (Koc), 74 wt.% in Brenntag Catalyst / diethylene glycol trimerization agent polycat® 203 Evonik Nitrogen catalyst dabco® 2040 1,2-Dimethylimidazole, 70 wt.% in ethylene glycol, Toyocat Evonik Nitrogen catalyst DM70 (70%) dabco® T120 di-n-butyl bis (dodecylthio) tin, dibutyltin dilauryl mercaptide, Evonik Metaa l catalyst Fomrez® UL-54 Dimethyltin bis (2-ethylhexyl thioglycolate) + Galata Metal catalyst methyltintriisooctyl thioglycolate Chemicals solstice® LBA trans-1-chloro-3,3,3-trifluoropropene Honeywell Liquid blowing agent Solstice® GBA trans-1,3,3, 3-tetrafluoropropene Honeywell Gaseous blowing agent DMDEE 2,2'-dimorpholinodiethyl ether Huntsman Nitrogen catalyst Dabco® LK221E non silicone surfactant Evonik Structuring agent / foaming stabilizer Ethacure® 100-LC Diethyltoluene diamine Albemarle Chain extender alcoholic alcohol / catalyst Polycatylamine IPKyl-methyl-polymer-Orange-TB-catalyst ® Milliken Colorant X96 Chemicals Suprasec® 5025 polymeric MethylDiphenylDi-isocyanate Huntsman Polyisocyanate / Crosslinkers Dabco TMR 7 50% solution of tetramethylammonium 2,2-Evonik Nitrogen n agent Examples 1-23 To determine the shelf life profile of the different polyol components, fresh and aged st Prepare ales of various polyol components according to the protocol described below and one or more of the following reaction parameters were determined: Gel time (GT): Period starting from the mixing of the isocyanate and polyol components until the moment when, if a wooden chopstick is inserted into the reaction mixture to a depth of 10m and pulled out, the reaction mixture deposited on the chopstick appears fibrous / congealed or the chopstick hits a solid core. Frequency of insertion in approximately 1 time per second.
Tack-Free Time (TFT): Period starting from the mixing of the isocyanate and polyol components until the moment when, when a protected finger is brought into contact with the surface of the reaction mixture, it appears non-stick on the protected finger. Frequency of insertion in approximately 1 time per second.
Sample preparation protocol: Polyol component: The polyol component was prepared by combining different ingredients (shown in the following tables) in a glass bottle that is closed to prevent product loss. If a liquid blowing agent is present in the polyol component, this ingredient is added last. The gassing blowing agent (Solstice GBA) is not added. The resulting mixture is homogenized by vigorous manual shaking and allowed to stand at room temperature (room temperature, RT) for approximately 4 hours. Fresh samples: 30.0g of polyol component was transferred into a disposable 250cc coated paper ice cream cup and an amount of suprasec 5025 (a polymer MethylDiphenylDi-isocyanate) was added so that the reaction mixture has the ISO index shown in the tables below. The ISO index is defined as NCO / (OH + NH) multiplied by 100, ie the ratio of the number of isocyanate groups in the reaction mixture to the number of alcohol and amine groups in the reaction mixture, multiplied by 100. The ISO index of the examples was calculated as the ISO index that would have been obtained when the full polyol component (including Solstice GBA) were mixed at a 1: 1 volume ratio with an isocyanate component consisting of 90 wt.% suprasec 5025 and 10 wt.% Solstice GBA unless stated otherwise. The contents of the beaker are mixed with a hand mixer (Huvema HU 13 Laserdrill with attached 60 mm diameter propeller paint mixer) at 2500-3000 rpm for 5s at room temperature (23 ° C + 2 ° C) without application of heating or cooling. After 5 + 1 seconds, mixing is stopped, the mixer is removed from the beaker and one or more of the parameters described above are determined.
Aged samples: 40g of freshly prepared polyol component as described above (i.e. without gassing blowing agent) is transferred into a tin aerosol can. This can is closed with an aerosol tap and then the gaseous blowing agent (Solstice GBA) is added through the tap. This steel is shaken vigorously by hand and aged in an oven at 50 ° C. After aging, the steel is vigorously manually agitated and degassed (Solstice GBA removal) and allowed to cool and stabilize for about 4 hours at room temperature. After degassing / stabilization period, the can is pierced and 30g of the aged liquid is poured into a disposable cup. Then an amount of suprasec 5025 (a polymer MethylDiphenyIDi-isocyanate) is added corresponding to the ISO index shown in the tables below. The ISO index is defined as NCO / (OH + NH) multiplied by 100, ie the ratio of the number of isocyanate groups in the reaction mixture to the number of alcohol and amine groups in the reaction mixture, multiplied by 100. The ISO index of the examples was calculated as the ISO index that would have been obtained when the full polyol component (including Solstice GBA) were mixed at a 1: 1 volume ratio with an isocyanate component consisting of 90 wt.% suprasec 5025 and 10 wt.% Solstice GBA. The contents of the beaker are mixed with a hand mixer (Huvema HU 13 Laserdrill with attached 60 mm diameter propeller paint mixer) at 2500-3000 rpm for 5s at room temperature (i.e. without adding heating or cooling). After 5 seconds, mixing is stopped, the mixer is removed from the beaker and one or more of the parameters described above are determined.
Comparative example 1 Comparative example 2 eyoempoet | __ | Demn | @ | ww | «Ë |» | wa | © | © | w @ | > ema | @ ® | # | # 8 | # | ne Brakes |] Aged-4 days 50 ° C me] Li |:
a: calculated as the ISO index that would have been obtained when the full polyol component (including Solstice GBA) were mixed at a 1: 1 volume ratio with an isocyanate component consisting of 93.81 wt.% suprasec 5025 and 6.19 wt.% Solstice GBA.
Comparative Example 3 Comparative Example 4 Comparative Example 5 ee TTT] ET | 83 [am] © æ] »vw.
Bismuth
ER ES [ve | 7 8] € |] = | ww. jeune | = | = m | | = R, [see | 8 8] +3 8] 8 | [ver | = (==) @ 188] = = (ww | __ | obsolete-4 ne OO Reael) | NA more | B [B | a me | | a IE a: calculated as the ISO index that would have been obtained if the full polyol component (including Solstice GBA) were mixed at a 1: 1 volume ratio with an isocyanate component consisting of 93.81 wt.% suprasec 5025 and 6.19 wt. % Solstice GBA. b: all samples contain precipitate after 7 days at 50 ° C, indicating the degradation of reagents | Comparative example 6 Take comparative example 7 |. © | (we | ® | 8 | + | @ | (ver | 5 | 88 | 5 | = w |
| Comparative example 6 Comparative example 7 [Sect LA | 9 | 88 | 37 | 157 | es | Aged-2 days and Aged-7 days ee an] am |] a: calculated as the ISO index that would have been obtained if the full polyol component (including Solstice GBA) were mixed at a 1: 1 volume ratio with an isocyanate component consisting of 93 , 81 wt.% Suprasec 5025 and 6.19 wt.% Solstice GBA Example 8 Example 9 Example 10 [Pre | TS [em | @ | @ | 8 | 8 vw [mets | 0æ [om |> œ [18 ] 8 | 0m. Your - | 8 | 58 | w |
TTT Obsolete-3 ame | Obsolete-7 ame |
Example 8 Example 9 Example 10 Aged - 2 months at room temperature pr | 8 | 98 | ww | example 11
CCE ECO [| Outdated-7 days
D Aged-14 days pe example 12 example 13 example 14 example 15 g n n n n example 12 example 13 example 14 example 15 Polyol men [me | EE to | Total 206.30 100.0 207.35 100.0 208.40 100.0 214.05 100.0 [| Sheet [TT] Tack Free Time 43 38 33 26 da Aged - 14 days Tack Free Time 34 32 29 25 AA ... TFT Rise -20% -16% 4% h OL Aged - 21 days He Tack Free Time 34 33 33 23 Ee TFT Rise -21 % -13% -12% u OO 1 TT | example 16 example 17 Li
| example 16 SSS ET [ve | vw | Par | 09 | 00 | +0 | 7w | (ea |. | Obsolete-7 days ee Obsolete-14 days we Da Tram [| Obsolete-21 days ee In the following examples 19 and 20, TBNPA was first dissolved in part of TCPP, so that a 50 wt.% solution of TBNPA in TCPP was obtained and the resulting solution was used in forming the polyol component.
| example 18 example 19 example 20 Povorempame [| wa [| mrs [te | 50 | e =] nw [|
| example 18 example 19 example 20 ÿ # wr | __ | ces) rer Aged-7 days 50 ° C ee) And Aged-14 days 50 ° C ee) Rest Geo Aged-28 days 50 ° C No) Rest Geo TFT song 09 In the following examples 21 and 22, the nitrogen catalyst was added at least partially as the corresponding ammonium ion by mixing amounts of water, amine and acid listed in the table below and homogenizing before addition to the remainder of the polyol component. In Example 21, the water, amine, and succinic acid were heated to 50 ° C to provide a homogeneous solution. In the following Examples 21 and 22, TBNPA was first dissolved in a portion of TCPP to obtain a 50 wt.% Solution of TBNPA in TCPP and the resulting solution used in forming the polyol component.
In the following Examples 21 and 22, Reactint Orange X96 was first dissolved in a portion of TCPP to obtain a 2.44 wt.% Solution of Reactint Orange X96in TCPP and the resulting solution was used in forming the polyol component.
In Example 23, the nitrogen catalyst is a quaternary ammonium compound (tetramethylammonium) added as a salt with succinate by first adding the amount of the commercially available catalyst Dabco TMR-7 listed in the table below with a small amount of water and the amount of succinic acid listed in the table below. The resulting solution is used in the formation of the polyol component.
Example Example 21 Example 22 Example 23 Composition Parts by weight Parts by weight
Example Example 21 Example 22 Example 23 poa | [| 5 [5 | 0m | Dae [To | 800 | 0m 10m | 4 »| @ | Ramos | on [oa | 0% | 95 | 0m | few [| a | em [se | w | | fveme | 60 | zer | 60 [8 | 0m | [more | 2 (A | 000 [ame | 08 | 08 Foe | [oe [9 [or | 0 »| ww |
CI Obsolete-7 days ee Obsolete-14 ame Obsolete-28 ame I 1: Example 23 is aged at 40 ° C. As apparent from the above examples, the polyol components in accordance with the invention (Examples 9-23) exhibit excellent shelf-life stabilities, as demonstrated using various concentrations of different ingredients and additives commonly used to provide a commercially useful foam.
Examples 24-28 The polyol components in the tables below were prepared as a kit to form a spray foam. The kit consists of a first pressurized aerosol can containing an isocyanate component consisting of 90 wt.% Isocyanate and 10 wt.% Solstice GBA and pressurized to 6 bar using compressed air.
e a second pressurized aerosol can which may contain a polyol component as described in the previous examples and which is pressurized to 6 bar using compressed air.
The kit was connected by hoses (1 for each can) with a spray gun. When the system is activated, both compounds are delivered in a 1: 1 volume ratio and mixed with a static mixer. The “free-foam-density” of the foam produced is measured.
The “free-foam-density” is determined as follows: a sample is cut from the sprayed foam when it is fully cross-linked (after about 1h) and the dimensions and mass of the foam piece are measured. The density can be calculated.
Preparation of samples The isocyanate component is prepared by transferring an amount of isocyanate into a tin aerosol can which is then closed with a tap. This connection is pressurized with a gaseous blowing agent and compressed air to 6-7 bar.
The polyol component is prepared by adding various ingredients (without the liquid blowing agent if present) into a disposable 250 cc coated paper ice cream cup. The mixture is homogenized with a hand mixer (Huvema HU 13 Laserdrill with attached 60 mm diameter propeller paint mixer) at 2500-3000 rpm until homogeneous. When the mixed polyol is homogeneous, an amount is transferred to a tin aerosol can. Then the liquid blowing agent is added and the can is closed with a tap. This compound is pressurized with the gaseous blowing agent and pressurized to 6 bar by addition through the tap.
The polyol component is combined with the isocyanate component and sprayed according to the spraying procedure. Aging Procedure Samples are prepared in the same manner as described above, except that the polyol component is pressurized with only the gassing blowing agent (and not the compressed air). The resulting aerosol can is aged in an oven at 50 ° C for a specified period of time. After this aging period, steel is removed from the furnace and cooled to room temperature for 24 hours before being pressurized with compressed air to 6 bar.
40
The aged polyol component is combined with the non aged isocyanate component and sprayed according to the spraying procedure. Spraying Procedure An unaged isocyanate component is combined with a fresh or aged polyol component by means of a spray gun. Both components are shaken vigorously before spraying. The gun is activated and the foam is distributed until the cans are empty. Results: In the following Examples 24-28, the nitrogen catalyst is added at least in part as the corresponding ammonium ion by mixing amounts of water, amine and acid listed in the table below and homogenized before addition to the remainder of the polyol component.
In the following Examples 24-28, TBNPA was first dissolved in a portion of TCPP to obtain a 50 wt.% Solution of TBNPA in TCPP and the resulting solution used in forming the polyol component.
In the following Examples 24-27, Reactint Orange X96 was first dissolved in a portion of TCPP to obtain a 2.44 wt.% Solution of Reactint Orange X96in TCPP and the resulting solution was used to form the polyol component.
Comparative Comparative Comparative Example 27 Example 28 Example 24 Example 25 Example 26 Composition Weight wt. Weight wt. Weight wt. Weight SD wt. Weight wt. ng parts% parts% parts% elen. % share. % Polyol component 62.50 27.2 62.50 27.1 62.50 27.7 62.50 27.2 62.5 28.8 Z425 3 1 5 3 4 37.50 16.3 37.50 16, 2 37.50 16.6 37.50 16.3 37.5 17.3 PA240 4 7 5 4 0 Struksilon 6.25 2.88 8026 30.00 13.0 30.00 13.0 30.00 13. 3 30.00 13.0 40 18.4 TCPP 7 1 2 7 5 React shade 0.31 0.13 0.31 0.13 0.31 0.14 0.31 0.14 Orange X96 em | se [za] em | 260 | ow [266 | sm | z | »|)
LULU UN 7
Comparative Comparative Comparative Example 27 Example 28 example 24 example 25 example 26 40.00 17.4 40.00 17.3 40.00 17.7 40.00 17.4 40 18.4 owe) OE ee amberzu 2.55 1 , 11 2.55 1.11 2.55 1.11 1.35 0.62 ee EI TE TEE Dioctyltindila 1.95 0.85 ee [EE | Bismuth 3.00 1.30 aen [OI | [race | oe [ce] ce [on] 20 [| 0m [9m] 9 [7 Total 229.48 100, 230.53 100, 225.21 100, 229.48 100, 216.7 100 [a [| | | | ea [|] Tack-free time Not measured 127 52 44 we EYE YEN ES density Not measured 34.5 29.4 27.0 27.0 Ee ee OT LE YEN ES Thermal Not measured 28.8 21.4 20.7 Not determined conductivity id (mW / m: K) Obsolete-7 ae Tack-free time 130 290 150 46 Not determined
PH TFT rise 128% 188% 4% Not determined on density 31.58 33.70 26.7 Not determined a 1 | TT and 1 TON TT As is apparent from the above examples, the polyol component in accordance with the invention exhibits excellent shelf life stability, and the spray foam prepared using the polyol component in accordance with the invention has and / or retains excellent density and / or thermal conductivity properties. Example 29 The polyol components from the table below were prepared as a kit to prepare a spray foam. The kit and spraying procedures are described in Examples 24-28 except that the cans were pressurized to 17 bar with nitrogen gas (instead of 6 bar with air). The test was performed on a scale of 12kg (combined weight of both components).
In the following Example 30, TBNPA was first dissolved in a portion of TCPP to obtain a 50 wt.% Solution of TBNPA in TCPP and the resulting solution used in forming the polyol component.
In the following examples, Reactint Orange X96 was first dissolved in a portion of TCPP to obtain a 2.44 wt.% Solution of Reactint Orange X96 in TCPP and the resulting solution was used in forming the polyol component. | Example 29 Particles per wt.% Composition wt.
Peace | EE | ew | > # | ven | Aged - 34 days at room temperature (23 ° C + 2 ° C) As can be seen from Example 29 above, the polyol component according to the invention shows excellent shelf life stability, and the spray foam prepared with the polyol component according to the invention has and / or retains excellent density and / or thermal conductivity properties.

权利要求:
Claims (17)
[1]
A polyol component suitable for producing a two-component polyurethane foam wherein the polyol component comprises a polyol, a gaseous hydrohalolefin blowing agent, a nitrogen catalyst and a tin catalyst, the tin catalyst comprising a sulfur atom, the gaseous hydrohalolefin blowing agent being selected from 1.3 , 3,3-tetrafluoropropene (HFO 1234ze); 2,3,3,3-tetrafluoroprop-1-ene (HFO 1234yf); 1,2,3,3,3-pentafluoropropene (HFO 1225ye); 1,1,3,3,3-pentafluoropropene (HFO 1225zc); 1,1,2,3,3-Pentafluoropropene (HFO 1225yc) or combinations thereof.
[2]
The polyol component of claim 1, wherein the polyol is selected from the group consisting of a sucrose-containing polyol; phenol, a phenol-formaldehyde-containing polyol; a glucose-containing polyol; a sorbitol-containing polyol; a methyl glucoside-containing polyol; an aromatic polyester polyol; an aliphatic polyester polyol; an aromatic polyether polyol; an aliphatic polyether polyol; a polybutadiene polyol; a polycaprolactone polyol; a polycarbonate polyol; a hydroxyl terminal polyolefin polyol; a graft polyol; glycerol; ethylene glycol; diethylene glycol; propylene glycol-containing polyol; graft copolymers of polyether polyols with a vinyl polymer; a copolymer of a polyether polyol with a polyurea; one or more of (a) condensed with one or more of (b): (a) glycerin, ethylene glycol, diethylene glycol, trimethylol propane, pentaerythritol, soybean oil, lecithin, tall oil, palm oil, castor oil; (b) ethylene oxide, propylene oxide, a mixture of ethylene oxide and propylene oxide; or combinations thereof, preferably a sucrose-containing polyol.
[3]
The polyol component according to claim 1 or claim 2, comprising a polyether and / or polyester polyol in an amount greater than 50 wt% based on the total weight of polyol present in the polyol component, preferably greater than 70 wt%, preferably more than 85 wt%, preferably more than 95 wt%, preferably more than 98 wt%, preferably more than 99 wt%.
[4]
The polyol component according to any one of claims 1-3 comprising aliphatic polyether polyols, aliphatic polyester polyols, aromatic polyester polyols and combinations thereof in an amount greater than 50 wt.% Based on the total weight of polyol present in the polyol component, at preferably more than 70 wt%, preferably more than 85 wt%, preferably more than 95 wt%, preferably more than 98 wt%, preferably more than 99 wt%.
[5]
The polyol component of any one of claims 1 to 5 wherein the gaseous hydrohalolefin blowing agent is HFO 1234ze (E).
[6]
The polyol component according to any one of claims 1 to 5 wherein the polyol component also comprises a liquid hydrohalolefin blowing agent having a boiling point greater than 18 ° C at 1 atm, preferably HFO-1336mzz, HFO-1233zd or combinations thereof, preferably HFO- 1336mzz (Z), HFO-1233zd (E) or combinations thereof.
[7]
The polyol component according to any of claims 1-6 wherein the polyol component comprises halogenated non-hydrohalolefin blowing agents in an amount of less than wt%, preferably less than 5 wt%, preferably less than 1 wt%, at preferably 0 wt% based on the total weight of the polyol component.
[8]
8. The polyol component according to any one of claims 1-7, wherein the nitrogen catalyst is a sterically hindered amine catalyst or the corresponding ammonium ion, preferably a catalyst selected from the group of dicyclohexylmethylamine; ethyldiisopropylamine; dimethylcyclohexylamine; dimethylisopropylamine; methylisopropylbenzylamine; methylcyclopentylbenzylamine; isopropyl-sec-butyl-trifluoroethylamine; diethyl- (α-phenylethyl) amine, tri-n-propylamine, dicyclohexylamine; f-butylisopropylamine; di-t-butylamine; cyclohexyl-t-butylamine; di-sec-butylamine, dicyclopentylamine; di- (α-trifluoromethylethyl) amine; di- (α-phenylethyl) amine; triphenylmethylamine and 1,1-diethyl-n-propylamine, dimorpholinodiethyl ether, N-ethylmorpholine, N-methylmorpholine, bis (dimethylaminoethyl) ether imidazole, N-methylimidazole, 1,2-dimethylimidazole, dimorpholinodimethyl ether, N, N, N, N ' , N ", N" -pentamethyldiethylenetriamine, N, N, N ', N', N ", N" - pentaethyldiethylenetriamine, N, N, N ', N', N ", N" -pentamethyldipropylenetriamine, bis (diethylaminoethyl) ether , bis (dimethylaminopropyl) ether, the corresponding ammonium ion and combinations thereof.
[9]
The polyol component of any one of claims 1 to 7, wherein the nitrogen catalyst is a quaternary ammonium compound of the formula (NR'R ° R * R *) * wherein R ', R 2, R * and R * are each independently selected from comprises the group consisting of alkyl and alkenyl, preferably from the group consisting of methyl, ethyl and propyl, most preferably from the group consisting of methyl and ethyl.
[10]
The polyol component of claim 9 wherein the nitrogen catalyst comprises tetramethylammonium.
[11]
The polyol component according to any one of claims 1-10, wherein the tin catalyst is selected from the group of tin mercaptides, preferably dioctyltin dilauryl mercaptide, dimethyltin bis (2-ethylhexyl thioglycolate), dioctyltin bis (2-ethylhexyl thioglycolate), octyltin tris 2-ethylhexyl thioglycolate), dibutyltin bis (2-ethylhexyl thioglycolate), dimethyltin diisooctyl thioglycolate, methyltin triisooctyl thioglycolate, dimethyltin dilauryl mercaptide, dibutyltin dilauryl mercaptide, dimethyltin diisooctylmercaptide, dimethyltin diisooctyl thioglycolate, methyltin triisooctyl thioglycolate, dimethyltin dilauryl mercaptide, dibutyltin dilaurylmercaptide, dimethyltindilaurylmercaptide, and combinations thereof, preferably dimethyltindilaurylmercaptide, and combinations thereof, preferably dimethyltindilaurylmercaptide, dimethyltin diisooctyl thioglycolate, and combinations thereof 40
[12]
The polyol component of any one of claims 1-11 comprising 20 wt% to 95 wt%, preferably from 30 wt% to 60 wt%, and more preferably from 40 wt% to 50 wt% polyol based on the total weight of the polyol component; 5-50 wt%, preferably 10-30 wt%, preferably 15-25 wt% gaseous hydrohalolefin blowing agent based on the total weight of the polyol component; e 0.1-10 wt.%, preferably 0.5-7 wt.%, preferably 0.5-5 wt.% nitrogen catalyst based on the total weight of the polyol component; and a tin catalyst in an amount of 0.001-10 wt.%, preferably 0.005-5 wt.%, more preferably 0.01-2 wt.% of tin based on the total weight of the polyol component.
[13]
A two component polyurethane foaming kit, wherein the kit comprises an isocyanate component comprising a suitable isocyanate and an optional blowing agent; and a polyol component as defined in any one of claims 1-12.
[14]
The kit according to claim 13, wherein the isocyanate is selected from the group of aromatic diisocyanates, aromatic triisocyanates, aromatic tetraisocyanates, arylalkyl polyisocyanates, aliphatic polyisocyanates, polymethylene polyphenylisocyanates, alkylene diisocyanates, aromatic polyisocyanates and combinations. thereof.
[15]
A polyurethane foam made with a polyol component as defined in any one of claims 1-12.
[16]
The foam of claim 15 comprising a gassing hydrohalolefin in the cells of the foam, wherein the polyurethane foam has a free-rise core density of less than 35 kg / m3, less than 34 kg / m2, less than 32 kg / m *, less than 31 kg / m , less than 30 kg / m , less than 29 kg / m , less than 28 kg / m with a “free-rise core density” measured according to EN 1602.
[17]
A process for forming a foam comprising: e providing an isocyanate component comprising a suitable isocyanate and an optional blowing agent; e providing a polyol component as defined in any one of claims 1 to 12, and e mixing said isocyanate component and said polyol component to form the foam.

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同族专利:

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CA3096154A1|2019-10-10|

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AU2019249959A1|2020-11-12|

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CN112262166A|2021-01-22|

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KR20200141058A|2020-12-17|

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WO2019193178A1|2019-10-10|

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US20210155740A1|2021-05-27|

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BE1026148A1|2019-10-22|

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法律状态:
2020-08-26| FG| Patent granted|Effective date: 20200728 |

优先权:

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申请号 | 申请日 | 专利标题

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EP18166182.8A|EP3549967A1|2018-04-06|2018-04-06|Polyurethane foam forming compositions|

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