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    • 专利摘要:
    1471102 Polymerisation catalyst UPJOHN CO 15 Jan 1975 [30 Jan 1974] 1760/75 Heading B1E [Also in Division C3] A catalyst composition for the trimerisation of a polyisocyanate and of use in the formation of cellular polyisocyanurate polymers comprises (a) 10-90 mole % of a monomeric epoxide; (b) 5 to 75 mole % of a tertiary amine isocyanate-trimerisation catalyst containing a dimethylamino group; and (c) 5 to 80 mole % of a glycine salt of formula wherein: M is Li, Na or K; R 1 is H or C 1 -C 12 alkyl; R 2 is H, C 1 -C 12 alkyl or -CH 2 COOM; and R 3 is H or CH 2 N(R 2 )CH 2 COOM. Component (a) may be a glycidyl ether of a novolac resin, having a functionality of at least two or butyl-, octyl- or phenyl-glycidyl ethers. Component (b) may be N, N-dimethyl-ethanolamine, -benzylamine, -cyclohexylamine or -aminopropylamine; N, N-dimethyl-N', N'-bis- (beta-hydroxyethyl) propane diamine; N, N', N" - tris (dimethylaminopropyl) hexahydrotri - azine; 2, 4, 6-tris(dimethylaminomethyl) phenol; o-dimethylaminomethylphenol; p-dimethylaminomethylphenol; N, N, N', N'-tetramethyl- 1, 3-butanediamine or -propanediamine; or 2, 2'-bis(dimethylamino)diethyl ether. Component (c) may be sodium N-(2-hydroxy-5-nonylphenyl)methyl-N-methyl glycinate. The glycinate salt may be used as a solution in a diluent, e.g. a mixture of ethylene glycol and dimethylformamide. Specification 1471101 is referred to.
    公开号:SU897112A3
    申请号:SU762101940
    申请日:1976-05-05
    公开日:1982-01-07
    发明作者:Антони Колаковски Ричард；Юджин Реймоур Гарольд (Младший)；Абдул Рида Сэйх Аднан
    申请人:Дзе Апджон Компани (Инофирма)；
    IPC主号:
    专利说明:

    (54) METHOD FOR OBTAINING A FOAM PLATE WITH ISOCIANURATE LINKS IN A POLYMER CIRCUMS and especially | BUT for layered flooring. A known method for producing foam shale with isocyanurate units in a chain polymer by trimerization of a polyisocyanate in the presence of a polyol, a frothing agent and a trimerization catalyst, as ka-. A trinerization catalyst utilizes a mixture of one-dimensional epoxide and a tertiary amine, including those containing the dimethylamine group 1 — The foam obtained by this method has a high fire resistance. However, this method requires the development of a foaming process with the mixing of at least two polymerization reactions, namely the formation of isocyanurate, which arises during the homopolymerization of the isocyanate used, and the formation of a small amount of polyurethane obtained by the reaction of the polyol with the isocyanate. The disadvantage of the method lies in the difference in the rates of the two polymerization reactions: the formation of polyurethane begins before trimerization, which results in two separate elevated stages in the overall foam profile. When foams are produced in a high-speed mixer and distributed on a conveyor, a two-stage elevation in the mold causes the appearance of grooves: cropping. The latter term, horschio, is known when making foams, it refers to the movement of fresh liquid reagent flowing under the foam when it is already in the process of lifting, and the curing point itself is not reached. In this case, unequal surfaces and the inversion of the gel inside such a formation in the foam mass causes internal stresses that lead to cracks, on the surface of the mass, and to defects. The foam mass obtained by a known method has a maximum height of 45 cm. The two-stage elevating form is inconvenient because the inclination angle of the conveyor line relative to the horizon must be greater than for a simple increasing form, in order to partially reduce the problems arising from double lifting. Increasing the angle of motion of the foam mass presents additional difficulties. The purpose of the invention is to increase the height of the foam, accelerate the cure and improve the structure of the foam. This goal is achieved by the method of producing foam with isocyanurate units in the polymer chain by trimerization of the polyisocyanate in the presence of polyol, blowing agent, and trimerization catalyst, as a trimerization catalyst, a mixture of 0.01-0.06 eq per 1 eq. monomeric epoxide polyisocyanate, 0.001-0.02 equiv. on 1 ek of the role of the tertiary amine isocyanate, containing dimethylamine. group ,, and 0.001-0.0.2 eq. at 1 eq. polyisocyanate compounds of the general formula. OH R2 V (JH2-J - (} H2-COO M® U where M is an alkali metal; is hydrogen, alkyl with 1-12 carbon atoms; Rij is hydrogen, alkyl with 1-12 carbon atoms, —CIA -COO M Rj - vol.ol and -CHfj -N-CH COO M Preferably, the compound is an obgche of the formula: RjCH 2 -Jf - CHg-COO -M® a, used as a 25-75% solution in an organic solvent. The invention includes an advanced process for the preparation of a foam plaster, most of whose repeated polymeric compounds are isocyanurate. The components of the catalyst are displaced together during the reaction or immediately before the trimerization reaction As one of the var fs, the tertiary amine and glycine salt (compound of formula D) can be pre-mixed or preserved separately until the trimerization process of the invention is required. Glycine salt is obtained by Mannich reaction by displacing phenol 1. formaldehyde and glycine salt of alkali metal of the formula RQ, MH-CH -COO M (HI; where R / i, R 2 and M are as defined above. Phenol, p-cresol, m-butyl Lenol, p-heptylphenol, p-octylphenol, p-nonylphenol, p-decylphenol, p-dodecylphenol can be used as starting Lenol, as glycine salts. of formula III — sodium potassium glycinates, lithium, sodium M methylglycinate, potassium H methylglycinate, sodium H butyl glycinate, sodium M octyl glycinate, sodium H dodecyl glycinate, disodium iminodiacetate and similar to them. The molar ratio of phenol: fbop | maldehyde: glycine derivatives of formula III is from 1: 1: 1 to 1: 2: 2. In a preferred embodiment of the invention, glycerol salt is used in the catalyst in combination with a diluent, which uses low molecular weight polyols such as ethylene glycol, diethylene glycol, dipropylene glycol, dibutylene glycol, tetraethylene glycol. glycerin, liquid polyethylene glycols, such as polyoxyethylene glycols, cellosolvate, butyl cellosolvate, carbitol, methylcarbitol, ethanolamine diethanolamine, triethanolamine; and a dipolar solvent such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide and the like; and omesi any of these solvents. Ethylene glycol, diethylene glycol, polyethylene glycol and mixtures thereof are particularly preferred. “As an epoxide, any of mono- or polyepoxy | DOs can be used, which in combination with amine catalysts are used as catalysts for the trimerization of polyisocyanates. This polyepoxide uses a compound that contains many epoxy groups and does not include polymers that are obtained by polymerizing epoxy monomers partially or completely through epoxy groups. Any polyol known in the art can be used to prepare polyisocyanurate foams. The polyols can be introduced separately during the trimerization of a polyisocyanate, or they can be pre-reacted with a polyisocyanate to form a polyisocyanate (prepolymer with N-groups), which is then subjected to trimerization. As the polyisocyanates used to prepare the polyisocyanurate foams in accordance with the invention, any organic polyisocyanates commonly used for these purposes can be used. Polymethylene polyphenyl polyisocyanates are preferred. Compounds commonly used in this field can be used as foaming agents, dispersants, foam stabilizers, surfactants, flame retardants, etc. Especially preferred as flame retardants are phosphorus-containing additives, such as (2-chloroethyl) phosphate, tri (2-chloropropyl) phosphate, tri- (2,3-dibromopropyl) phosphate, tri- (1.3 dichloroisopropyl) - phosphate and the like. - Example 1. Rigid high-temperature resistant foams are obtained to compare the properties of foams at 148.9 ° C with dry aging in accordance with the invention, but in the absence of a dimethylamine group in the catalyst. In the example, the foam is produced by manual or machine offset as indicated below. When manually preparing the foam pre-mix the ingredients. Then the components are quickly poured into the box of a 17.5 x 17.5 x 27.5 cm car. To let the foam rise. In a machine process, the preparation of the foam components is mixed in a high-speed mixer and distributed along a conveyor line to obtain mass. Component I contains a polyisocyanate ingredient, including a surfactant, a blowing agent. The polyol portion of component 1I contains a surfactant (L-5340 and DC193), a foaming agent, an epoxy component of the catalyst and a component containing a tertiary amine and salt, glycinate Foams A (manual process) and W (machine process), obtained in accordance with invention, are given in table. 1 together with foam V (manual process) with catalyst of demethylamine component, and foam G (manual process) containing dimethylamine-containing catalyst. It can be seen that foams A and B have the highest stability at 148, with dry aging compared with foam C and D, which have lost their distinctive characteristics in their properties. To prepare foams A and B, polymethylene are used: Lenine isocyanates with a viscosity of about 650 cP at an equivalent of 140 (isocyanate 580); polymethylene polyphenyl isocyanate with a viscosity at 25 ° C of about 1500 cP and an equivalent of 14.0 is used to prepare foam G (- 18). The polyester used in Example 24.8 parts by weight of an esterification product is 1 mol of chloric anhydride with 1.1 mol of diethylene glycol and 2.5 mol of propylene oxide mixed with 8 wt, including the polyol formed by the interaction of 3 mol ethylene oxide with trimethylol propylene having an equivalent weight of about 93, and 2, 2 weight, diethylene glycol, the components of the compositions, their quantity and the properties of the foams obtained are given in Table 1. The composition of the catalytic mixture: per 1 eq, polyisocyanate, 0.0477 eq. Of epr oxide, tertiary amine, 0.0241 eq., glycine salt, 0.0034 equiv., Example 2. Rigid foams with high thermal stability were manually prepared as indicated in Reamer 1 using the same polyester components. For the preparation of foam plastic, polyisocyanate was used. the same as foam C in example 1, with an acidity of 0.07%, foam E - from using polymethylene polyphenyl isocyanate having an acidity of 0.13%. The components of the compositions and the number of the obtained foams are given in table. 2. At 1 eq. isocyanate, 0.0477 eq. epoxide, 0.0097 eq. tragic amine and 0.0093 eq. glycine salt. Example 3. High temperature resistant rigid foams are prepared by hand using the ingredients specified for foam B in example 1, except that the foam (c) is obtained without epoxy resin (DEN-431) in the combined catalyst. Properties of foams are given in table. 3 (foam plastic cracked, foam plastic no). Example 4. Foams are prepared by hand using the ingredients specified for foam B in example 1 to determine activity in the catalyst of the invention. a number of different a 1inov in combination with two other components of this catalyst. N, M-dimethylcyclohexylamine is substituted with the amines given in table. 4. Composition of the reaction composition, parts by weight: Component I Polyisocyanate 134 FurolCEF15 L-53401 Freon 11-B 15 Component II. Polyester35 DEN-43i8 DC-193. 1 Freon 11-B 15. 50% Component 111-3.8 weight.h. Sodium solution of —N- (2-hydroxy-5-noi. lphenyl) methyl-M-methyl glycinate in ethylene glycol mixed with .0046 eq. amine. The minimum prevalence in isocyanurate is 55%, and with dimethylcyclohexylamine - 70.6%. Example 5. Foams I, K, and M of this example (Table 5; exhibit enhanced performance. All foams are obtained by machine, with the exception of foam And, and in each case the catalyst is used in such concentrations to obtain the maximum high performance. N, N-dimethylcyclohexylamine and epoxide are used as components of the catalyst for foam preparation. The foam volume is not large. Foam K contains glycinamine catalyst mixture, but no epoxide, as a result, 45 foam m settles to 12.5 cm. A foam contained glycine and epoxy components, but no amine except the polyisocyanate is not processed length epoxide reduce its acidity This causes foam shrinkage.
    Characteristics of foams are given in table. 5. Example b. Foams H and O of this example, prepared by machine, are rigid foams and contain the overwhelming amount of polyisocerated bonds.
    Foam O can be obtained with a maximum lifting height (45 cm, with two separate steps visible in the raised profile. A stepwise increase in the shape of the foam leads to foam trimming and foam stratification.
    Foam H has a uniform increase,., Which prevents undercutting and foam is easily obtained with a height of 60 cm. Foam H forms much less dryness than foam O, as IT determined by testing A s TM E-34.
    Characteristics of foams are given in table. 6;
    Example 7. Foams are prepared as in example 1.
    The ingredients, their number, as well as the properties of the foams are given in table. 7
    The polyisocyanate used in this example is a polymethylene polyphenyl isocyanate mixture heated to nitrogen with sparging through it. The mixture contains approximately 30% by weight of methylene bis-phenyl isocyanate, the remainder of this mixture of polymethyl polyphenyl isocyanates with a functionality greater than 2, the isocyanate equivalent of 140.
    The polyester 35 parts by weight represents a blend consisting of 92% by weight. polyester polyol obtained by esterification of 1 mol of chlorendic anhydride with 1.1, mol of diethylene glycol and 2.5 mol of propylene oxide, and
    also from 8% by weight of diethylene glycol, a hydroxyl equivalent of 206,
    DMP-10 is a mixture of O-im-dimethylaminomethylphenol, nitrogen equivalent, 137.2.
    Catalyst A at 33.2 wt.%. is 2, b-bis (N-sodium carboxymethyl-N-methylaminomethyl) -phenol, dissolved in a mixture in a ratio of 35:65 of ethylene glycol and polyethylene glycol with a molecular weight of 400, equivalent to a weight of 277.
    Catalyst B 37% by weight is 2,6-bis (N, N-bis (sodium b: arboximethyl) -aminomethylJ-p-anarylphenol dissolved in a mixture of ethylene glycol and polyethylene glycol with a molecular weight of 400, equivalent weight, 175 .
    Smoke formation is a darkening in relation to the passage of light observed in the chamber where it is burned to release soot when a beam of light is applied to the photocell after a horizontal flame of 12.5x12.5x2.5 cm is directed to the center of a narrow flame. to burn the foam polymer for 1 min, followed by measuring the loss of transparency by the photoelectric method.
    The content of the three-dimensional structures in the foam is not a direct, but simple means of comparing the formation of the three-dimensional structures of a number of polyisocyanurate foams. These figures do not give an idea of the percentage of conversion of the isocyanate to the polyisocyanurate, but rather the weight percentage of the isocyanure ring of the total weight of the foam. For example, the reference sample on which the method of comparing peak values in the infrared spectrum is based is 1,3,5-triphenyl isocyanurate with 35%: three-dimensional c-structures, which reflects the relative weight percentage attributable to the isocyanurate ring while 65% are triphenyl rings.
    The relative percentage of the isocyanate ring to the foam weight is determined by the infrared spectrum of the foam as the difference between the absorption peak in the 1410 cm region (characteristic of the three-dimensional structure) and 1510 (characteristic of the aromatic ring) and by comparing this difference with the triphenyl isocyanurate curve (standard ),
    Thus, the implementation of the proposed method increases the height of the foam rise, accelerates
    0 curing and improving the structure of the foam. At the same time, foam plastic saves high fire resistance.
    Table 1.
    Component
    Polyisocyanate
    Isocyanate-580
    Component III
    «« «To Catalyst A
    1 shih
    AT
    ,
    , #
    D
    134
    134
    3.5
    10.5
    11.5
    Physical properties Density, kg / m
    Foaming characteristics of tris (betachloroethyl) phosphate. Epoxy Novolac resin - with viscosity
    fr
    Surface active agent.
     A mixture of 3 wt.h. A 50% aqueous solution of sodium-N- (2-hydroxy-5-nonylphenyl) methyl-N-methylglycinate in diethylene glycol with the weight.h. tetramethylpropanediamine.
     A mixture of 9 wt.h. 50% aqueous solution of sodium-N- {2-hydroxy-5-nonylphenyl) methyl-N-methylglycinate in diethylene glycol with 2 weight.h. dimethylcyclohexylamine. 50% solution of sodium-M-12-hydroxy-5-nonylphenyl) methyl-N-methylglycinate in diethylene glycol.
     10.5 parts by weight catalyst C mixed with 1.0 weight.h. diethylcyclohexyl.
    Component I
    Polyisocyanate (acidity 0.07%)
    Polyisocyanate (acidity 0.13%)
    L-5340
    FurolCEF flame retardant
    Freon 11-B
    Continued table. one
    35.9
    32.7
    Some Wrong Fitment Density Distribution. In Foam
    table 2
    134
    134 1
    15
    15
    20
    20 76.5 cp at 25s
    Component I I
    Polyester
    OEN-431
    OC-193
    Freon 11-B Component I I I
    Catalyst
    A mixture of 9 wt.h. 50% N 1 solution of N- (2-hydroxy-5-nenilnyenil)
    methyl-N-methylglycinate in diethylene glycol with 2 parts by weight diethylene glycol and 1 weight.h. tetramethylbutanediamine.
    35 8 1 10
    35 8 1 10
    component I
    Polyesocyanate
    L-5340
    FurolCEF flame retardant
    Freon 11-B omponent I I Polyester OEN-431 DC-193
    I
    freon 11-B component I I I Catalyst B Initiation first, s Elevation first, s Initiation second min: s Gel, min-s
    Increase second, min: s Without tack-free, min: s Cure, min: s
    Table 3
    134
    15
    sixteen
    35 8 1 10
    35
    3.5
    3.5
    sixteen
    sixteen
    50
    50
    One o'clock
    1:05
    1:05
    1:16
    1:40
    1:50
    Three o'clock
    3:15
    8: 006: 009: 00 7:00 Shrinkage no load no
    1789711218 AminI Trimer formation,% Nicotine 1 BFj ethylamine N, N-diethylcyclohexylamine. M-methyldiethanolamine. Triethanolamine-Nikvnn d-Picolin 2-Benyl pyridine., M-ethylformin. N-methylmormoline. 2, 4,6-Tris (dimethylaminomethyl) phenol I-Dimethylaminomethyl phenol M, M-Dimethyl-M, M, bis- (hydroxyethyl) diamine N, N-Dimethylethanolamine Tetramethylguanidine N, N-Dimethylbenzylate N, N, N, N -Tetramethyl-1,3-butyndiamine, N, N, N, N -Tetramethylpropanediamine Triethylenediamine N, N-Dimethylcyclohexylamine although the formation of a trimer is high, about the quality and its shrinkage
    Table 4
    i О 24.6 29.3 35.3 46.0 50.6 51.2 52, b 54.0 56.6 58.7 58.7 60.6 62.0 66.0 66.6 67.3 68.0 low
    Component I
    Polyeocyanate
    PAPI-18
    FurolCEF
    L-5340
    Freon 11-in Component II
    Polyester
    Polyester
    DEN-431
    OS-193
    Freon 11-B Component I I t
    N, N-dimethylcyclohexylamine Catalyst B

    Catalyst E
     #
    Catalyst F
    Foaming, with
    Initiation with
    MOVEMENT First, min: s Initiation second, min: s
    Table 5
    134
    134
    134
    134
    15 15
    15
    one
    35 35
    35
    6
    3.2
    10.5
    22
    22
    24
    24
    Increase, min: s
    Cure, min: s
     Polyester is obtained by esterification of 1 mol of chloric anhydride
    1.1 mol of diethyl glycol and 2.5 mol of propylene oxide. A mixture of 7,875 weight.h. A 50% aqueous solution of sodium-gmt (2-hydroxy-5-nonylphenyl) methyl-Ngmethylglycinate in diethyl glycol and 2.625 parts by weight diethylenglycol A mixture of 9 wt.h. 50% aqueous solution of sodium-N- (2-hydroxy-5-nonylphenyl) methyl-M - methyl glycinate in diethylene glycol with 1 weight.h. dimeticyclohexylamine and 1 weight.h. diethylenglycol
    Ingredient and physical property
    1 component I
    Polyisocyanate
    Polyisocyanate
    L-5340
    L-5420
    FuroICEF
    Continued table. five
    Six o'clock
    2:30 2:30
    8: 009: 00
     Table 6
    Formulation foam, weight.h. BUT
    134
    134
    Component II
    Polyester
    DC-193
    DEN-431
    Freon 11-B
    Hetrofoam-320

    DER-542
    Component III
    OMR-Yu
    Catalyst) E Foaming, with Initiation, with Gel, min: s Raising first, min: s
    Initiating the second and
    min: s
    Final min increase: s
    Otlip free, min: s. Mass height, cm
    Continued table. b
    43
    26 30 14
    26
    04
    06
    1:10
    1:15
    2: 40-3: 30 2: 20-2: 45
    2: 40-3: 15
    45
    60 And with Component 134 -134 134 Polyisocyanate L-5340 15 15 FurolCEF 22. 22 Freon 11-B
    Component II
    35
    Polyester 15 22
    35
    35
    35
    35 - 35 Ngredient and physical property Formulation. Foam, weight, h. Test: ASTME-84. Formation of smoke from. 2.5 cm2525 Lifting foamNo undercut- Crop ,. Polyisocyanate is obtained by heating polymethylene polyphenyl isocyanate containing about 50% by weight,% methylene (phenyl isocyanate), viscosity at 25 ° C, 250 cps, at 235C and 1000 cP. Solid urethane foam polyfirpolyol based on chloride, acid, hydroxyl number 320 320. The condensation product of tetrabromobisphenol A. And epichlorohydrin, the percentage of bromine 44-48%, epoxy equivalent weight 350-400 .. A mixture of o- and-dimethylaminomethylphenol. and C a 7 redient and physical Formulation foam, weight, h; Realty ,, Continued table. 6 N I O Zany foam caused cracking due to two increases. ..l ..-. Iul - .. L.-LL. ± L..l 134 134 134 134 134 15 22 (0.001 (0.008 (0.001 (0.001 (0.02 eq) eq) eq) eq) equivalent to 0.31 catalyst
    Diethylene glycol (catalyst diluent
    The periods of reaction stages, min: s
    07
    Mixing
    08
    The rest
    Initiation first, 11
    50
    Boost first
    Initiation of the second 1:25
    Continued table. 7
    1 (0.004 eq) 0.069 0.015 0.068 0.084 0.071
    Continued table. 7
    权利要求:
    Claims (2)
    [1]
    1. The method of obtaining foam with isocyanuate units in the polymer chain by trimerization of polyisocyanate in the presence of a polyol, a foaming agent and a trimerization catalyst, characterized in that, in order to increase the height of the foam, accelerate curing and improve the structure of the foam while maintaining high fire resistance A mixture of 0.01.0.06 eq is used as a trimerization catalyst. at 1 eq. monomeric epoxide polyisocyanate, 0.001-0.02 eq. at 1 eq. a tertiary amine polyisocyanate containing a dimethylamine group, and 0.001 : -0.02 eq. at 1 eq. polyisocyanate compounds of General formula I.
    HE
    CH 2 - & G-CH 2 - C00®M
    Κι
    VNIIPI Order 11752/47. Circulation 511
    40
    45
    50
    55
    60
    where M is an alkali metal;
    K 4 - hydrogen, alkyl with 1-12 carbon atoms;
    Cd - hydrogen, alkyl with 1-12 carbon atoms, -CHL-COO®M®; Cd
    - hydrogen and -CH ^ -Y-SND-COSPM®
    [2]
    2. The method according to claim 1, characterized in that the compound of the general formula
    Ν ^ -Ν-ΟΗ ^ -ΟΟΟθ-ΙΛ®
    used in the form of a 25-75% solution in an organic solvent.
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    同族专利:
    公开号 | 公开日
    AU7717575A|1976-07-08|
    JPS50114393A|1975-09-08|
    GB1471102A|1977-04-21|
    BE825014A|1975-07-30|
    US3903018A|1975-09-02|
    DE2502331C3|1981-02-26|
    IT1029400B|1979-03-10|
    DD121120A5|1976-07-12|
    SU786862A3|1980-12-07|
    DD121123A5|1976-07-12|
    DE2502331B2|1980-06-26|
    CA1037646A|1978-08-29|
    JPS543717B2|1979-02-26|
    DE2502331A1|1975-08-07|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
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    US3299137A|1962-09-25|1967-01-17|Union Carbide Corp|Acyclic hydrocarbon aldehyde carbamoyl oximes|
    US3476933A|1966-10-21|1969-11-04|Westinghouse Electric Corp|Large-celled polyurethane foam|
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    优先权:
    申请号 | 申请日 | 专利标题
    US437779A|US3903018A|1974-01-30|1974-01-30|Novel cocatalyst system for trimerizing polyisocyanates|
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