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    • 专利摘要:
    The present invention relates to a silicone—modified vegetable oil—based polyol as well as its preparation method and application. The preparation steps of the silicone— modified vegetable oil—based polyol are: N— (B—aminoethyl)—y— aminopropylmethyldimethoxysilane (KH—602) and epoxy eleostearate monoglyceride With an epoxy value of 3% are mixed at a molar ratio of its epoxy groups and KH—602 = 2: l~3:l and have a ring—opening reaction to form a silicone modified vegetable oil— based polyol. A compound polyol can be prepared by evenly mixing the silica microcapsule flame retardant and polyether polyol Which is partially replaced With the above—mentioned silicone modified vegetable oil—based polyol. The compound polyol can be used to prepare polyurethane (PU) foam. The PU foam prepared this way has good mechanical properties, thermal stability and flame retardancy, and its limiting oxygen index can reach 23.5%.
    公开号:NL2026927A
    申请号:NL2026927
    申请日:2020-11-19
    公开日:2021-07-28
    发明作者:Zhang Meng；Zhou Yonghong；Jia Puyou；Feng Guodong；Hu Lihong
    申请人:Inst Of Chemical Industry Of Forestproducts Caf；
    IPC主号:
    专利说明:

    1 AO 20.11.1090 NL A silicone-modified vegetable oil-based polyol as well as its preparation method and application Technical Field The present invention belongs to the technical field of polyurethane foam, specifically related to a silicone-modified vegetable oil-based polyol as well as its preparation method and application. Background Technology Polyurethane (PU) is a class of compounds with a poly (carbamate) structure prepared mainly from polyols and polyisocyanates. It is widely used in coatings, adhesives, elastomers, foams and other materials. Traditional raw materials for the PU production are mainly derived from non-renewable petrochemical resources. At the same time, due to the rising crude oil prices as well as the increasingly worsening of the greenhouse effect, environmental pollution and other global problems, the use of renewable resources to replace petrochemical resources for the preparation of PU materials has attracted the attention of scientific researchers, and this is also one of the future development trends.
    As a renewable resource, vegetable oil has become an important source of multifunctional monomers and oligomers in PU synthesis due to its rich sources, stable biodegradability, low price, low toxicity and renewable characteristics. The principle of synthesizing vegetable oil-based polyols is to use unsaturated double bonds and carboxyl ester groups in vegetable oil to convert vegetable oils into polyols through hydrolysis, transesterification, saponification, hydrogenation, epoxidation and amination. PU foam prepared with vegetable oil-based polyols has good chemical and physical properties, especially having good hydrolysis resistance and thermal stability. PU has low density but a large specific surface area, and there are a lot of hydrocarbon chains in its structure. This makes PU foam extremely easy to burn. Because reactive flame retardants and inorganic flame retardants containing phosphorus, nitrogen, silicon and other flame retardant elements have low toxicity, environmental friendliness and
    2 AO 20.11.1090 NL other characteristics, they are widely used in the preparation of flame retardant PU foam. However, adding high doses of inorganic flame retardants into PU foam not only increases the production cost of PU foam, but also reduces the physical properties of PU foam.
    Content of the Invention Technical problem needed to be solved: In order to improve the flame retardancy, mechanical properties and thermal stability of PU foam, the present invention provides a silicone-modified vegetable oil-based polyol as well as its preparation method and application. The present invention uses renewable tung oil as a raw material and makes it undergo a series ofreactions and then makes the resultant have a ring-opening reaction with N-(B-aminoethy1)-y-aminopropylmethyldimethoxysilane (KH-602) to produce flame-retardant tung oil-based polyol (PTOK). Since nano-silica is directly used as the reinforcing component of PU foam, this can usually cause the agglomeration of the initial nano-scale dispersion phase. Ammoniummolybdate is used as the shell of the material and nano-silica is used as the core materialto form ammonium molybdate- coated silica. Silica microcapsule flame retardant is compounded with tung oil-based flame-retardant polyol and commercially available polyether polyol (PPG4110) to obtain compound polyol. A new type of PU foam is obtained by reacting compound polyol with isocyanate. The PU foam has a limiting oxygen index of up to 23.5%and a compressive strength of up to 613.7 KPa. The initial thermal degradation temperature of the PU foam tends to decrease with the increase in the amount of silica microcapsule flame retardant in the PU foam.
    Technical solution: A silicone-modified vegetable oil-based polyol, whose structural formula is as follows:
    3 AO 20.11.1090 NL 0 OH i AAA]
    OH < ne Ho meo HN R= wl NVA < OCH; H;CO=si—0CH, CH; ‚ Wherein
    ANNES R= NH Si—CH; OCH, The preparation method of silicone-modified vegetable oil-based polyol mentioned is characterized by the following steps: N-(B-aminoethy])-y- aminopropylmethyldimethoxysilane (KH-602) and epoxy eleostearate monoglyceride with an epoxy value of 3% are mixed at a molar ratio of its epoxy groups and KH-602 = 2:1-3:1 and have a ring-opening reaction to form a silicone modified vegetable oil- based polyol.
    Application of the above-mentioned silicone modified vegetable oil-based polyol in the preparation of PU foam. The specific application method is as follows: first mix the combined polyol, silica microcapsule flame retardant and additives together to form a compound polyol, and then mix the resulted compound polyol with isocyanate for 20-30s at a speed of 2000- 2500r/min; pour the resulted mixture into the mold, and then cure it for 12 hours. In the mixture, various ingredients have the following parts by mass: the combined polyol has 100 parts, silica microcapsule flame retardant 0-20 parts, and isocyanate 118 parts; and the composition of additives are (in parts by mass): PU foam stabilizer 3.0-4.0 parts, water 0.4 ~0.6 parts, forming agent 15-25 parts, and catalyst 0-0.20 parts. The active ingredient of the above-mentioned combined polyol is silicone-modified vegetable oil- based polyol.
    4 AO 20.11.1090 NL The above-mentioned silica microcapsule flame retardant is formed with ammonium molybdate-coated silica. Weigh a proper amount of silica and ammonium molybdate each and dissolve them in a phosphoric acid solution and mix them evenly, and then add nitric acid into the resulted mixture solution dropwise and adjust the pH of the mixture solution to 1.0. After standing still for some time, the mixture solution is filtered. The solid product obtained by the filtration is washed and dried. After all these operations, the finally obtained solid is silica microcapsule flame retardant, which has an average particle size of 19 um. The above-mentioned isocyanate is polymethyl polyisocyanate PAPL The above-mentioned PU foam stabilizer is silicon foam stabilizer 5501. The above-mentioned forming agent is HFC-365mfc.
    The above-mentioned catalyst is dibutyl tin dilaarate. Beneficial results: The polyol obtained by the reaction of epoxy eleostearate monoglyceride and KH-602 at a certain proportion by using tung oil as the raw material is a type of flame retardant polyol with a reactive structure and has high thermal stability, strong reactive activity and high hydroxyl value. A compound polyol can be prepared by evenly mixing the silica microcapsule flame retardant and polyether polyol which is partially replaced with the above-mentioned silicone modified vegetable oil- based polyol. The compound polyol can be used to prepare PU foam. The PU foam prepared this way has good mechanical properties, thermal stability and flame retardancy, and a limiting oxygen index of up to 23.5%. The obtained silicone-modified tung oil-based polyol has a hydroxyl value of 344.71 mgKOH/g, a silicon content of
    1.00%. a nitrogen content of 1.00%, an acid value of less than 1.30 mgKOH/g and a moisture content of less than 0.10%, and is suitable for the preparation of PU foam.
    Brief Description of the Drawings
    AO 20.11.1090 NL Fig. 1 is the infrared spectrum of epoxy eleostearate monoglyceride. In the spectrum, 3400 cm-1 is the vibration absorption peak of -OH; 2920 cm-1 and 2860 cm-1 are the stretching vibration absorption peaks of methyl and methylene, respectively; 1730 cm-1 is the stretching vibration absorption peak of C=O; 1460 cm-1 and 1370 cm-1 are the 5 flexural vibration absorption peaks of methyl groups; 1240 cm-1, 1170 cm-1 and 1100 cm-1 are the stretching vibration absorption peaks of C—O in monoglyceride; 1050 cm- 1 is the characteristic absorption peak of the C—O—C ether bond; and 908 cm-1 is the characteristic absorption peak of the epoxy group.
    Fig. 2 is the infrared spectrum of KH-602 modified tung oil-based polyol. 3440 cm-1 is the characteristic absorption peak of -OH and -NH; 2920 cm-1 and 2850 cm-1 are the stretching vibration peaks of methyl and methylene groups, respectively; 1740 cm-1 is the characteristic absorption peak of the ester bond in the eleostearate monoglyceride skeleton; 1460 cm-1 and 1370 cm-1 are the flexural vibration absorption peaks of the methyl group; 1240 cm-1, 1170 cm-1 and 1040 cm-1 are the stretching vibration absorption peaks of C-O; 987 cm-1, 823 cm-1, 731cm-1 and 693cm-1 are the characteristic absorption peaks of Si-C and Si-C, indicating that KH-602 has successfully been integrated into the epoxidation eleostearate monoglyceride structure.
    Fig. 3 is the infrared spectrum of the silica microcapsule flame retardant. 3226 cm-1 is the hydrogen bond absorption peak of N—H; the peak near 1632 cm-1 is the bending vibration peak of HOH in water; 795 cm-1, 584 cm-1, 570 cm-1 and 547 cm-1 are the symmetric stretching vibration absorption peaks of the Si—O bond.
    Embodiments The following text gives a further description of the present invention in combination with some embodiment cases. The “Ge” in the present invention represents a mass fraction.
    The present invention carries out a series of modifications to tung oil to obtain KH-602 modified tung oil-based polyol. The prepared structural flame-retardant tung oil-based polyol is further foamed with commercially available polyether polyol, silica
    6 AO 20.11.1090 NL microcapsule flame retardant, additives and polyisocyanate through a one-step method to obtain the silicone modified tung oil-based PU foam enhanced with the silica microcapsule flame retardant.
    The main solution includes the following two aspects: I. Method for preparing the above-mentioned KH-602 modified tung oil-based polyol. The eleostearate monoglyceride containing epoxy groups is obtained by modifying the eleostearate bond and the double bond. The primary amino group in the structure of KH-602 has active reactivity and can have ring-opening reaction with epoxy groups. The reaction equation is:
    H aren tl No OH OCH; |, ot = & Lor TY on > R= WIA, OCH; wo ae CH; Equation 2: The ring-opening reaction of epoxy eleostearate monoglyceride and KH- 602 A more specific preparation method is, in parts by mass: take 100 parts of epoxidation eleostearate monoglyceride and 7.94 parts of KH-602, mix them and then heat them to 60-70°C, and then let them react for 2-3 hours under nitrogen protection to get a brown liquid, which is the silicone-modified tang oil-based polyol.
    The hydroxyl value of the silicone-modified tung oil-based polyol prepared according to the present invention is measured with the the phthalic anhydride esterification method specified in GB/T 12008.3-2009; its acid value is measured with the method specified in GB/T 12008.5-2010; and its viscosity is measured with the rotational viscometer method specified in GB/T 12008.7-2010.
    7 AO 20.11.1090 NL II. Silicone modified tung oil-based PU foam enhanced with the silica microcapsule flame retardant:
    1. Composition of compound polyol, in parts by mass: (1) 25 parts of KH-602 modified tung oil-based polyol is, and 75 parts of polyether polyol (PPG4110). (2) 0-20 parts of silica microcapsule flame retardant.
    2. Composition of additives, in parts by mass: (1) Water: 0.30~0.70 parts by mass. (2) Forming agent: 25 parts by mass.
    (3) Foam stabilizer: silicone foam stabilizer 5501: 3.75 parts by mass. (4) Catalyst: Dibutyl tin dilaurate: 0~0.20 parts by mass.
    3. Silicone modified tung oil-based PU foam enhanced with the silica microcapsule flame retardant: See Table 1 and Table 2 for the preparation formula and performance test results of PU foam. Use compound polyol and isocyanate as the main raw materials.
    The specific operation procedure is as follows: Mix the compound polyol and additives uniformly while rapidly stirring them, and then rapidly stir the resulted mixture with isocyanate for 20~30s at a speed of 2000~2500 r/min, and then pour the resulted mixture into the mold, and then cure it for 12 h.
    The isocyanate 1s PAPI, and its trade name is PM-200 from Yantai Wanhua Polyurethane Co., Ltd.
    8 AO 20.11.1090 NL The present invention prepares silica microcapsule flame retardant from ammonium molybdate-coated silica to form a silicon-nitrogen-molybdenum flame-retardant system. At the same time, by using tung oil as the raw material, it obtains silicone-modified reactive tung oil-based flame-retardant polyol (PTOK) through transesterification, epoxidation and ring-opening reactions. Petroleam-based polyol (PPG4110) partially replaced by PTOK is compounded with the silica microcapsule flame retardant to form a compound polyol, which is used as one of the raw materials for preparing PU foam. The flame retardant PU foam prepared by adding silica microcapsule flame retardant into PU foam has excellent mechanical properties and flame retardant effects. A proper amount of silica microcapsules can promote the dehydration of PU foam into char during the combustion process and dilute flammable gases. At the same time, due to the coating and barrier effect of the carbon layer, PU foam can exhibit excellent gas and solid phase flame retardant effects.
    The present invention discloses methods for preparing a series of silicone modified tung oil-based PU foam enhanced with the silica microcapsule flame retardant. Compared with PU foam prepared from commercially available polyether polyols, the silicone modified tung oil-based PU foam enhanced with the silica microcapsule flame retardant has excellent flame retardancy and mechanical properties, but its initial decomposition temperature decreases.
    Embodiment case 1 Mix epoxy eleostearate monoglyceride and N-(B-aminoethyl)-y- aminopropylmethyldimethoxysilane (“KH-602" for short) at a molar ratio of nepoxy group : nKH-602 = 7:3, and heat the mixture to 70°C and react for 2h ander nitrogen protection to get silicone modified tung oil-based polyol. According to the formula shown in Table 1, mix 100 parts (by mass) of PPG4110 and additives uniformly, and then mix the resulted mixture with 118 parts (by mass) of isocyanate for 20~30s at a speed of 2000~2500 r/min, and then pour the obtained mixture into the mold and cure it at 60°C for 12 h in a blast drying oven.
    Embodiment case 2
    9 AO 20.11.1090 NL Mix epoxy eleostearate monoglyceride and N-(B-aminoethyl)-y- aminopropylmethyldimethoxysilane (“KH-602” for short) at a molar ratio of nepoxy group : nKH-602 = 7:3, and heat the mixture to 70°C and react for Zh under nitrogen protection to get silicone modified tung oil-based polyol. According to the formula shown in Table 1, mix 25 parts (by mass) of KH-602 modified tung oil-based polyol with 75 parts (by mass) of PPG4110 and additives uniformly, and then mix the resulted mixture with 118 parts (by mass) of isocyanate for 20~30s at a speed of 2000~2500 r/min, and then pour the obtained mixture into the mold and cure it at60°C for 12h in a blast drying oven.
    Embodiment case 3 Mix epoxy eleostearate monoglyceride and N-(B-aminoethyl}-y- aminopropylmethyldimethoxysilane (“KH-602" for short) at a molar ratio of nepoxy group : nKH-602 = 7:3, and heat the mixture to 70°C and react for 2h under nitrogen protection to get silicone modified tung oil-based polyol. According to the formula shown in Table 1, mix 25 parts (by mass) of KH-602 modified polyol with 75 parts (by mass) of PPG4110, 7.5 parts (by mass) of silica microcapsule flame retardant and additives uniformly, and then mix the resulted mixture with 118 parts (by mass) of isocyanate for 20~30s at a speed of 2000~2500 r/min, and then pour the obtained mixture into the mold and cure it at 60°C for 12 h in a blast drying oven. Embodiment case 4 Mix epoxy eleostearate monoglyceride and N-(B-aminoethyl)-y- aminopropylmethyldimethoxysilane (“KH-602" for short) at a molar ratio of nepoxy group : nKH-602 = 7:3, and heat the mixture to 70°C and react for 2h ander nitrogen protection to get silicone modified tung oil-based polyol. According to the formula shown in Table 1, mix 25 parts (by mass) of KH-602 modified polyol with 75 parts (by mass) of PPG4110, 10.90 parts (by mass) of silica microcapsule flame retardant and additives uniformly, and then mix the resulted mixture with 118 parts (by mass) of isocyanate for 20~30s at a speed of 2000~2500 r/min, and then pour the obtained mixture into the mold and cure it at 60°C for 12 h in a blast drying oven.
    10 AO 20.11.1090 NL
    Embodiment case 5
    Mix epoxy eleostearate monoglyceride and N-(B-aminoethyl)-y-
    aminopropylmethyldimethoxysilane (“KH-602" for short) at a molar ratio of nepoxy group : nKH-602 = 7:3, and heat the mixture to 70°C and react for 2h under nitrogen protection to get silicone modified tung oil-based polyol.
    According to the formula shown in Table 1, mix 25 parts (by mass) of KH-602 modified polyol with 75 parts (by mass) of PPG4110, 17.5 parts (by mass) of silica microcapsule flame retardant and additives uniformly, and then mix the resulted mixture with 118 parts (by mass) of isocyanate for 20~30s at a speed of 2000-2500 r/min, and then pour the obtained mixture into the mold and cure it at 60°C for 12 h in a blast drying oven.
    Table 1 Silicone modified tung oil-based PU foam enhanced with silica microcapsule (in parts by mass)
    Embod og ope PUfam Silica iment 4110 OK Catalyst PAPI stabilizer Water 6e microca case 5501 psule
    1 100 0 015 118 375 031 25 0 2 75 25 0 118 3.75 0.55 25 0 3 75 25 0 118 3.75 0.56 25 7.50 4 75 25 0 118 3.75 0.62 25 10.90 5 75 25 0 118 3.75 0.62 25 17.50
    Table 2 Silicone modified tang oil-based PU foam enhanced with the silica microcapsule flame retardant {the test method refers to the national standard) Embodimentease 1 2 3 4 5 “Foam density /kg.m™ 58355 59.95 6148 6227 6491 Compressive strength /KPa ~~ 150.9 253.6 381.1 458.9 613.7 Thermal decomposition temperature PC 282.20 277.50 271.47 25405 261.59 Oxygen index /% 19.0 20.1 22.4 23.0 23.5
    11 AO 20.11.1090 NL Vegetable oil-based polyol synthesized from renewable tung oil can partially replace petroleum-based polyol PPG41 10 for the production of PU foam.
    This can ease the PU industry's dependence on petroleam-based polyols.
    Adding an appropriate amount of silica microcapsule flame retardant into PU foam can improve the mechanical strength and flame retardancy of PU foam, and also has a certain effect on the smoke suppression of PU foam.
    权利要求:
    Claims (9)
    [1]
    1. A silicon-modified vegetable oil-based polyol, which is characterized by the following structural formula: 0 OH AeA AAA]
    OH
    NH HO
    S ANAS HN R= NH SCH < OCH; H3;CO~Si-OCH; H; ‚ where AN H;CO R= NH VN den OCH,
    [2]
    A silicon-modified vegetable oil-based polyol preparation method according to claim 1, which is characterized by the following steps: N-(B-aminoethyl)-y-aminopropylmethyldimethoxysilane (KH-602) and epoxy eleostearate monoglyceride having an epoxy value of 3% are mixed in a molar ratio of its epoxy groups and KH-602 = 2:1 ~ 3:1 and have a ring opening reaction to form a silicon-modified vegetable oil-based polyol.
    [3]
    Use of the silicon-modified vegetable oil-based polyol according to claim 1 in the manufacture of PU foam.
    [4]
    Use according to claim 3, characterized in that first the combined polyol, the silica microcapsule flame retardant and additives are mixed together to form a composite polyol, and then the resulting composite polyol with isocyanate for 20-30 seconds at a rate of 2000 - 2500 r/min is mixed, the resulting mixture is poured into the mold where it
    13 AO 20.11.1090 NL then cures for 12 hours, whereby in the mixture different ingredients have the following parts by mass: the combined polyol has 100 parts, the silica microcapsule flame retardant 0 - 20 parts and isocyanate 118 parts, and the parts of the additives: PU foam stabilizer 3.0 - 4.0 parts, water 0.4 ~ 0.6 parts, molding agent 15 ~ 25 parts, and catalyst are 0 ~ 0.20 parts, wherein the active ingredient of the above-mentioned combined polyol is a silicon-modified polyol based on vegetable oil.
    [5]
    Use according to claim 4, characterized in that the above-mentioned silica microencapsulation agent flame retardant is formed with ammonium molybdate-coated silica wherein an appropriate amount of each of silica and ammonium molybdate is weighed and dissolved in a phosphoric acid solution and mixed uniformly, then adding to the resulting mixture solution nitric acid is added dropwise and the pH of the mixture solution is adjusted to 1.0, after which the mixture solution is filtered after standing still for some time, the solid product obtained by the filtration is washed and dried and after all these operations finally the solid silica microcapsule flame retardant with an average particle size of 19 µm is obtained.
    [6]
    Use according to claim 4, characterized in that the above-mentioned catalyst is dibutyltin dilaurate.
    [7]
    Use according to claim 4, characterized in that the above-mentioned PU foam stabilizer is silicon foam stabilizer 5501.
    [8]
    Use according to claim 4, characterized in that the above-mentioned isocyanate is polyarylpolymethyleneisocyanates (PAPI).
    [9]
    Use according to claim 4, characterized in that the above-mentioned forming agent is HFC-365mfc.
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
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