CN1639240A - Catalyst combination for increasing trimer content in foam - Google Patents

Catalyst combination for increasing trimer content in foam Download PDF

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Publication number
CN1639240A
CN1639240A CNA028293312A CN02829331A CN1639240A CN 1639240 A CN1639240 A CN 1639240A CN A028293312 A CNA028293312 A CN A028293312A CN 02829331 A CN02829331 A CN 02829331A CN 1639240 A CN1639240 A CN 1639240A
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China
Prior art keywords
polyvalent alcohol
catalyzer
dimethylamino
isocyanic ester
amine
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CNA028293312A
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Chinese (zh)
Inventor
R·A·小格里格斯比
R·L·齐默曼
E·L·小里斯特
P·G·H·J·沙弗约
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Huntsman Specialty Chemicals Corp
Huntsman Petrochemical LLC
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Huntsman Petrochemical LLC
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Publication of CN1639240A publication Critical patent/CN1639240A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1825—Catalysts containing secondary or tertiary amines or salts thereof having hydroxy or primary amino groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/09—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture
    • C08G18/092—Processes comprising oligomerisation of isocyanates or isothiocyanates involving reaction of a part of the isocyanate or isothiocyanate groups with each other in the reaction mixture oligomerisation to isocyanurate groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/161—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22
    • C08G18/163—Catalysts containing two or more components to be covered by at least two of the groups C08G18/166, C08G18/18 or C08G18/22 covered by C08G18/18 and C08G18/22
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/225—Catalysts containing metal compounds of alkali or alkaline earth metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0025—Foam properties rigid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0083—Foam properties prepared using water as the sole blowing agent

Abstract

Provided herein are compositions which are useful as catalysis in the production of polyisocyanurate foams. The compositions of the invention comprise N, N,N'-trimethylaminoethyl-ethanolamine in combination with one other catalysts useful in promoting trimerization of isocyanates. By promoting trimerization, isocyanate content of the foam is decreased which leads to a foam having better burn properties over prior art isocyanurate foams. Decreasing the isocyanate content of a foam should also lead to quicker de-mold of a molded foam becauses of reduced stickiness.

Description

Improve the catalyst composition of trimer content in the foams
Technical field
The present invention relates to be used to produce the catalyst composition of polyurethane-based foam body product, more specifically relate to promotion isocyanate trimerization catalyst for reaction composition in the production process of polyisocyanurate foam the finished product.
Background technology
Compound N, N, N '-trimethylammonium amino ethyl ethanolamine (CAS#2212-32-0) is used as catalyzer in the production of the polyurethane-based foam body product of being everlasting, the reaction between one or more hydroxyl groups that exist in the precursor with the isocyanate groups that promotes to exist in one or more isocyanic ester and formation urethane.N, N, N '-trimethylammonium amino ethyl ethanolamine can be by HuntsmanPetrochemical Corporation, Austin, Texas is commercially available with trade(brand)name JEFFCAT  Z-110, and it has following structure:
(CH 3) 2NCH 2CH 2N(CH 3)CH 2CH 2OH。
We know that this catalyzer can cause small part isocyanate groups and other isocyanate groups reaction of existence and the trimer of formation trimer such as MDI that exists in the polyurethane precursor material.But the trimerization reaction that is taken place is not sufficient to make the reaction general trend or uses the physical properties generation considerable change of the polyurethane foam products that this catalyzer produces.Usually, this material is used as " kicker " in foams, and like this application mainly is in order to promote the reaction between isocyanic ester and the water, thereby original position produces gas CO 2, and this CO 2As whipping agent.Have been found that it has very little activity (referring to J.Cell Plastic Vol.37, page 75) to the formation that promotes isocyanuric acid ester.
It is believed that producing a large amount of isocyanuric acid esters (trimer of isocyanic ester) group in foams can improve the combustioncharacteristics of isocyanuric acid ester foams.It is believed that in addition the isocyanate content that reduces foams can cause molded foam demoulding rapidly because of the viscosity of its reduction, and improve its physical properties.But mention in the prior art and use mixed catalyst disclosed herein system and do not promote how trimeric formation, making us especially is that every kind of composition itself can not promote trimeric formation significantly in the described mixed catalyst system curiously.
Summary of the invention
The invention provides a kind of catalyst composition that is used for forming polyisocyanurate foam by isocyanic ester and polyvalent alcohol.This catalyst composition comprises: comprise N, N, the amine component of N '-trimethylammonium amino ethyl ethanolamine; And trimer catalyst component.The present invention also provides a kind of method for preparing the isocyanuric acid ester foam product, comprises step: isocyanic ester and polyvalent alcohol a) are provided; B) provide whipping agent; C) provide catalyzer, described catalyzer comprises: i) comprise N, N, the amine component of N '-trimethylammonium amino ethyl ethanolamine and ii) trimer catalyst component; With d) in the presence of catalyzer and whipping agent, isocyanic ester is contacted with polyvalent alcohol.
Description of drawings
In the accompanying drawings:
Fig. 1 is given in a plurality of differences that contain and measures trimeric content in the generation foam formulation of catalyst compositions;
Fig. 2 is given under three different index levels and measures the raising that forms trimer content in the reaction process in the generation foam formulation of catalyst compositions at foams in a plurality of differences that contain;
Fig. 3 is given under three different index levels and measures the reduction that forms isocyanate content in the reaction process in the generation foam formulation of catalyst compositions at foams in a plurality of differences that contain;
It is to form the raising of trimer content in the reaction process at 200 o'clock in a plurality of generation foam formulation that contain different amount catalyst compositions at foams that Fig. 4 A is given in the index level;
It is to form the raising of trimer content in the reaction process at 300 o'clock in a plurality of generation foam formulation that contain different amount catalyst compositions at foams that Fig. 4 B is given in the index level;
It is to form the raising of trimer content in the reaction process at 500 o'clock in a plurality of generation foam formulation that contain different amount catalyst compositions at foams that Fig. 4 C is given in the index level;
It is to form the reduction of isocyanate content in the reaction process at 200 o'clock in a plurality of generation foam formulation that contain different amount catalyst compositions at foams that Fig. 5 A is given in the index level;
It is to form the reduction of isocyanate content in the reaction process at 300 o'clock in a plurality of generation foam formulation that contain different amount catalyst compositions at foams that Fig. 5 B is given in the index level;
It is to form the reduction of isocyanate content in the reaction process at 500 o'clock in a plurality of generation foam formulation that contain different amount catalyst compositions at foams that Fig. 5 C is given in the index level.
Embodiment
The invention describes us by making up the benefit that JEFFCAT  Z-110 (N, N, N '-trimethylammonium amino ethyl ethanolamine) and trimer catalyst such as potassium octanoate are found.With respect to other known catalysts of similar applications, the conversion that this as can be seen combination makes isocyanate groups be converted into isocyanurate group (being obtained in the reaction of foams by isocyanic ester) obviously improves.When carrying out according to the present invention, total utilising efficiency of isocyanic ester is improved.
Known when foams are in the open flame, the higher foams " burning property " that can cause usually of the content of isocyanuric acid ester (or trimer) group reduce in the final foams, and this is regarded as the non-flame properties that foams have improvement usually.Higher isocyanate conversion speed also can cause rigid polyisocyanurate insulation foam to have improved K-factor drift.It is believed that this be since in the foams formation amount of carbonic acid gas reduce cause unreacting isocyanate wherein amount still less.
Have been found that if the temperature of foams is raise or allow it to be increased to definite temperature, JEFFCAT  Z-110 shows unique unexpected behavior, and promptly the catalysis isocyanate trimerization is corresponding isocyanuric acid ester (producing more trimer groups in the foams) rapidly.Also find sylvite and the more isocyanuric acid ester of JEFFCAT  Z-110 combination results (trimer) group in addition, and compare with the catalyzer of prior art, the isocyanate content of using the fresh urethane foam that this catalyst composition produces reduces simultaneously.Therefore, observed the catalyst composition that comprises JEFFCAT  Z-110 and other trimer catalyst and had synergy at aspect of performance, in system, will further promote the formation of isocyanuric acid ester as catalyzer, and reduce the content of isocyanic ester with this composition.
The present invention uses JEFFCAT  Z-110 and at least a trimerization reaction promotes catalyzer.JEFFCAT  Z-110 can be with other amine or tin catalyst or aforementioned substances arbitrary combination and applied in any combination.In addition, in prescription, also can there be known whipping agent, because using this whipping agent is known to those skilled in the art, described whipping agent is as whipping agent, the water that does not contain CFC, the whipping agent that contains HCFC and CFC, and pentane (comprising Skellysolve A, pentamethylene, neopentane, iso-pentane and composition thereof) is particularly preferred whipping agent.
In first group of test, on the probe of a heating, topple over a kind of reactive foams (comprising " A " of prescription and the mixture of " B " two kinds of components), wherein said probe is located on ReactIR  1000 instruments, described instrument is by Mettler-Toledo Corporation ofColumbus, and Ohio is commercially available.By this way, might collect the real-time FTIR data of reactive foam body.The probe of heating is from room temperature, the timed interval be soaring in 900 seconds with constant speed be 180 ℃.All foam formulation all prepare in an identical manner and topple over, and are applied catalyst component difference in the foam formulation, and its composition changes.Its raw polyol is that the B component prepares by mixing following material: 100 weight parts (" pbw ") STEPHANOL  PS-2352 and 20pbw EXXSOL  1600,2.5pbw B-8477 and 0.5pbw water.The B-8477 modified siloxane material that German Goldschmidt AG sells of serving as reasons.In raw polyol, add catalyzer and mix up to evenly.Then, contain the B component and the isocyanic ester RUBINATE  M blending of catalyzer.
Table I
Embodiment ?1 ?2 ?3 ?4 ?5 ?6 ?7 ?8 ?9 ?10 ?11
Raw polyol ?54.4 ?54.4 ?54.4 ?54.4 ?54.4 ?54.4 ?54.4 ?54.4 ?54.4 ?54.4 ?54.4
JEFFCATZF-20 ?0.5 ?- ?- ?- ?- ?- ?- ?- ?- ?- ?-
JEFFCATZF-10 ?- ?0.59 ?- ?- ?- ?- ?- ?- ?- ?- ?-
JEFFCATPMDETA ?- ?- ?0.36 ?- ?- ?- ?- ?- ?- ?- ?-
JEFFCATTR-90 ?- ?- ?- ?0.26 ?- ?- ?- ?- ?- ?- ?-
JEFFCATZ-110 ?- ?- ?- ?- ?0.46 ?- ?- ?- ?- ?- ?-
JEFFCATZR-50 ?- ?- ?- ?- ?- ?0.51 ?- ?- ?- ?- ?-
Catalyst-free ?- ?- ?- ?- ?- ?- ?0.00 ?- ?- ?- ?-
Potassium octanoate ?- ?- ?- ?- ?- ?- ?- ?0.38 ?- ?- ?-
Potassium acetate ?- ?- ?- ?- ?- ?- ?- ?- ?0.50 ?- ?-
JEFFCATZ-80 ?- ?- ?- ?- ?- ?- ?- ?- ?- ?0.50 ?-
JEFFCATZR-40 ?- ?- ?- ?- ?- ?- ?- ?- ?- ?- ?0.42
RUBINATEM ?85.7 ?85.7 ?85.7 ?85.7 ?85.7 ?85.7 ?85.7 ?85.7 ?85.7 ?85.7 ?85.7
Collect the online FTIR data of the mixture of and preparation described by the embodiment 1-11 of last Table I, wherein all umbers are weight part.With time is function, at about 1409cm -1Trimeric peak appears in the vicinity, as shown in Figure 1.As can be seen, trimer being formed the unique tertiary amine product that shows obvious influence is JEFFCAT  Z-110.The trimer that utilizes JEFFCAT  Z-110 to carry out is formed on and begins to take place after foams reach about 54 ℃ of definite temperature.Have only potassium acetate or potassium octanoate to show similar trimer and form, but it is in the time more early of reaction, and while generation when temperature is lower, this may show that it has the catalytic mechanism different with Z-110.
Carry out second experiment changing the index of foams, and potassium octanoate, trimerization reaction promote the composition of the JEFFCAT  Z-110 in catalyzer and the JEFFCAT  PMDETA (five methyl diethylentriamine) in first example and second example to be used as catalyzer.The index of isocyanic ester deutero-foams is recently represented with the quantity of the hydroxyl in isocyanate groups quantity and the applied polyvalent alcohol.For those skilled in the art, index 2.0 (being expressed as " 200 " sometimes) be often referred to concerning each-two-NCO group is arranged the OH group.Here use JEFFCAT  Z-110 and investigate other improvement whether isocyanate conversion and trimer formation can take place.It is 15 seconds that catalyst consumption makes the foaming time (cream time).
Main polyvalent alcohol blend is used the specified material preparation of following amount:
STEPHANOLPS?2352???????????100.0pbw
GENETRON141B???????????????27.2pbw
TEGOSTADB-84PI?????????????2.0pbw
Water 0.5pbw
Two kinds of catalyst compositions of test are used the specified material preparation of following amount:
The catalyst A catalyst B
Potassium octanoate 89.7pbw potassium octanoate 89.7pbw
JEFFCATPMDETA??10.3pbw?????JEFFCATZF-110???10.3pbw
Following Table II is the amount that obtains required above-mentioned every kind of catalyst composition of 15 seconds foaming time:
Table II
Embodiment 12 13 ?14 ?15 ?16 ?17
Polyvalent alcohol blend (g) 38.9 38.9 ?38.9 ?38.9 ?38.9 ?38.9
RUBINATEM 38.7 38.7 ?57.8 ?57.8 ?96.9 ?96.9
Catalyst A (g) 0.45 - ?0.65 ?- ?0.78 ?-
Catalyst B (g) - 0.55 ?- ?0.70 ?- ?1.0
Index 200 200 ?300 ?300 ?500 ?500
The foaming time (second) 15 15 ?15 ?15 ?15 ?15
Silk gel time (second) 45 35 ?36 ?34 ?45 ?34
The no agglutinating time (second) 66 52 ?51 ?51 ?58 ?43
The increase time (second) 89 ?87 ?79 ?79 ?88 ?78
" foaming time " is meant that from isocyanic ester and polyol component initial mixing to being visually perceptible for the time that foams are spent beginning to react, the evidence that wherein begins to react is to have bubble to produce." silk gel time " is meant from isocyanic ester and polyol component initial mixing to extracting the time that be spent the raw material thread out from the reaction foams." no tack time " was meant from isocyanic ester and polyol component initial mixing to the time that does not have material to be spent reaction foam surface bonding.The time that " increase time " is spent being meant and stopping further to expand from isocyanic ester and polyol component initial mixing to foams.
In case it is 15 seconds necessary conditions that every kind of composition has been determined to make the foaming time, then represent the fresh reactant foam body of every kind of prescription will be dumped in the cup, measure heat release, and be recorded in the FTIR equipment from the cup center.Every kind of prescription is collected separately exotherm, and be used for making the heated probe sequencing of FTIR instrument subsequently.Before the FTIR heated probe is implemented test, 8 ounces of dixie cups in one inch hole at the bottom of placing a cup, the top of heated probe are arranged.Dixie cup at the top of probe to 1 inch of lower slip.Utilize the front to use the collected temperature curve of special formulation then with the heated probe sequencing.The mixing tank of using a 3500rpm is pre-mixed B component and 5 seconds of catalyzer of being added.In cup, add RUBINATE  M isocyanic ester then.Meanwhile, when beginning to mix, the FTIR instrument begins to collect data.Make foams mix for 7 seconds, be poured into the probe tip of heating then, thereby liquid is covered on the top surface of probe.Collected the FTIR data then 1000 seconds, and during this period of time, collected 552 spectrum, the heating curve wherein of heated probe following the procedure input simultaneously along band.
The FTIR spectrum that collection obtains is so also analyzed.Peak-peak is converted into data, and exports EXCEL  data sheet and drawing to.The peak curve of gained provides in Fig. 2 and Fig. 3.Fig. 2 has provided the influence to the trimer amount found of catalyzer and foams index in foams.With potassium octanoate applied in any combination JEFFCAT  Z-110, in all index tests, can both observe trimer content higher in the foams.It is the disappearance of function isocyanic ester that Fig. 3 has provided with catalyzer and index.Here show once more that the catalyst system that contains JEFFCAT  Z-110 has more effectively utilized the isocyanic ester in the foams than the system that does not contain JEFFCAT  Z-110.These illustrated results show that JEFFCAT  Z-110 has significantly improved trimeric content in the foams, and have improved the total conversion rate of isocyanate groups in the foams.
In the 3rd group of test, to use the hydrocarbon blowing agent that is known as EXXOL  1600 and prepare poly-isocyanurate (" PIR ") foams, described hydrocarbon blowing agent is commercially available by Exxon chemical company, and it contains the mixture of pentamethylene and iso-pentane.The prescription and the growth curve of foams provide in following table, and in all forms here, all umbers are weight part:
Table III
Embodiment 18 ?19 ?20 ?21 ?22 ?23
?STEPHANOLPS ?2352 25.48 ?25.48 ?24.1 ?24.1 ?21.54 ?21.54
?B-8477 0.51 ?0.51 ?0.48 ?0.48 ?0.43 ?0.43
Water 0.13 ?0.13 ?0.16 ?0.16 ?0.22 ?0.22
?EXXOL1600 5.66 ?5.66 ?7.02 ?7.02 ?9.57 ?9.57
Catalyst A 0.50 ?- ?0.62 ?- ?0.75 ?-
Catalyst B - ?0.70 ?- ?0.75 ?- ?1.12
?RUBINATEM 32.7 ?32.7 ?48.1 ?48.1 ?77.2 ?77.2
Index 200 ?200 ?300 ?300 ?500 ?500
The foaming time (second) 15 ?15 ?15 ?15 ?15 ?15
Silk gel time (second) 50 ?32 ?55 ?44 ?105 ?62
The no agglutinating time (second) 67 ?42 ?110 ?65 ?165 ?117
The increase time (second) 98 ?66 ?97 ?87 ?140 ?102
The foams of Table III are poured on the FTIR probe in identical mode noted earlier.The result of trimer absorption peak develops with Fig. 4 A, 4B and the illustrated mode of 4C.The result of isocyanic ester specific absorption provides in Fig. 5 A, 5B and 5C.
(A) component of using in prescription or isocyanate component can be made up of any amount of suitable aromatics or aliphatic group isocyanic ester, prepolymer or quasi-prepolymer, may use catalyst composition of the present invention in the wherein said prescription.Concerning those skilled in the art, they are isocyanate compositions of standard.Preferred example comprises MDI benchmark prepolymer, as those by Huntsman International, RUBINATE  M, RUBINATE  1850, RUBINATE  9480, RUBINATE  9484 and RUBINATE  9495 that LLC. is commercially available.Aromatic polyisocyanate such as tolylene diisocyanate, ditan-4,4 '-positional isomers of vulcabond and aforementioned substances; The polymeric isocyanic ester is as polymeric MDI and analogue; Aliphatic polymeric isocyanate such as hexamethylene diisocyanate and analogue; Alicyclic polymeric isocyanate such as isophorone diisocyanate and analogue; The prepolymer that has a terminal isocyanate groups as by above-mentioned substance and polyol reaction and toluene diisocyanate prepolymer that obtains and ditan-4,4 '-diisocyanate prepolymer; The isocyanic ester of sex change such as carbon imide sex change material; And other blended polymeric polyisocyanate.The isocyanic ester of using in component (A) can comprise US4, the aliphatic isocyanate type of describing in 748,192.They comprise aliphatic vulcabond, and the trimerization or the biuret form of aliphatic vulcabond more specifically, as the difunctional monomer of hexamethylene diisocyanate or tetraalkyl Xylene Diisocyanate, as tetramethylxylene diisocyanate.Cyclohexyl diisocyanate also is considered to useful aliphatic isocyanate.Other useful aliphatic polymeric isocyanate is at US 4,705, states in 814.They comprise aliphatic vulcabond, for example have the alkylidene group vulcabond of 4-12 carbon atom in alkylidene group, as 1, and 12-dodecane vulcabond and 1,4-tetramethylene diisocyanate.Also useful have an alicyclic diisocyanate, as 1,3 and 1, and 4-cyclohexyl diisocyanate, and any mixture of these isomer, 1-isocyanide acyl-3,3,5-trimethylammonium-5-isocyanide acyl methylcyclohexane (isophorone diisocyanate); 4,4 '-dicyclohexyl methane diisocyanate, 2,2 '-dicyclohexyl methane diisocyanate two and 2,4 '-dicyclohexyl methane diisocyanate and corresponding isomer mixture and analogue.
Comprise preparing other amine catalyst component of using as component in the foams according to the present invention: JEFFCAT  TAP, JEFFCAT  ZF-22, JEFFCAT  DD, tetramethyl butane diamine, dimorpholino diethyl ether, JEFFCAT  MEM, JEFFCAT  MEM DM-70, two (dimethylamino ethoxy) ethane of JEFFCAT  MEM, JEFFCAT  NMM, JEFFCAT  NEM, JEFFCAT  PM, JEFFCAT  M-75, JEFFCAT  MM-20, JEFFCAT  MM-27, JEFFCAT  DM-22, five methyl diethylentriamine, tetramethylethylened, tetramethyl-aminopropyl acid amides, 3-dimethylamino-N, N-dimethyl propyl acid amides, TMR , TMR  2, TMR  3, TMR  4 or known for a person skilled in the art any known substance that can in polyurethane system, be used as foaming or gel catalyst, but be not limited to this.Aforesaid all JEFFCAT  trademark materials all can be by Huntsman Petrochemical Corporation, 7114 North LamarBoulevard, and Austin, Texas obtains.TMR  is Allentown, the Air Products and Chemicals of Pennsylvania, the registered trademark of Inc.
Be used to provide the polyvalent alcohol of foams of the present invention to comprise aromatic polyester polyvalent alcohol, amino polyol, Mannich polyvalent alcohol, sucrose deutero-polyvalent alcohol, sorbyl alcohol deutero-polyvalent alcohol, polyether glycol, polymer polyatomic alcohol and have the polyester polyol of two or more reactive hydroxyls.Polyether glycol comprises polyhydroxy-alcohol such as glycol, glycerine, tetramethylolmethane and sucrose; Aliphatic amine compound such as ammonia and ethyleneamines; Aromatic amine compound such as tolylene diamine and ditan-4,4 '-diamines; And/or in the mixture of above-claimed cpd, add oxyethane or propylene oxide and the polyether glycol that obtains.The example of polymer polyatomic alcohol has described polyether glycol and ethylenically unsaturated monomer such as divinyl, vinyl cyanide and cinnamic reactor product, and there is enforcement down in the described catalysts for radical polymerization that is reflected at.Polyester polyol comprises the material that those are produced by diprotic acid and polyol reaction, for example poly-ethylidene adipic acid ester and poly-ethylidene terephthalate, and it can comprise the material that those reclaim from refuse.The arbitrary combination of aforementioned substances also can be used as polyvalent alcohol.
The example that is used for whipping agent of the present invention has lower boiling hydrocarbons such as pentane, halohydrocarbon, carbonic acid gas, acetone and/or water.Known methyl halide and halo ethane can be used as halohydrocarbon.Wherein preferred chlorine fluorinated hydrocarbon compound is as the single fluoromethane (R-11) of trichlorine, dichlorotrifluoroethane (R-123), dichloro list fluoroethane (R-141b), R-134A, R-141B, R-245fa and analogue.The consumption of foaming agent is not done concrete qualification, but is benchmark with 100 weight part polyvalent alcohols, and the consumption of chlorine hydrofluoric ether is not more than 35 weight parts usually, is preferably the 0-30 weight part, and the consumption of water is not less than 2.0 weight parts, is preferably the 3.0-20.0 weight part.Stablizer is selected from nonionic surface active agent such as organic polysiloxane poly (oxyalkylene) base co-polymer, silicone-diol copolymer and analogue or its mixture.The amount of stablizer is not done concrete qualification, but is benchmark with the polyvalent alcohol of 100 weight parts, it typically is about 0-2.5 weight part.
According to the present invention,, can add other auxiliary agent if wish or necessity.They comprise flame retardance, tinting material, filler, oxidation retarder, ultraviolet screening agent and to analogue well known by persons skilled in the art.
Can be flexible foam, HR foams, semi-rigid foam body, rigid foam, fine-celled foam body, elastomerics and use the analogue that known conventional once-forming method, prepolymer process and similar approach prepare by using the urethane foam that amine catalyst of the present invention prepares.In these known methods, particularly preferably be by using the method that foaming agent prepares urethane foam, wherein said foaming agent is treated to the array configuration with other material, as paillon foil, coating or border material or integration mold.Other material described here comprises resin such as polyvinyl chloride (PVC) RESINS, ABS resin, polycarbonate resin and analogue, metal, glass and analogue.The example application of the foam product of the present invention preparation comprises the internals of automobile, as panel board, seat, headrest, handrail and door-plate, and product of wrapping material, continuous laminating method, metal decking coating or the like.
Weight with 100 parts of polyvalent alcohols is benchmark, and the amount of the amine catalyst of using in composition is 0.02 to 10 weight part, and more preferably 0.1 to 5 weight part wherein can prepare foams according to the present invention by described composition.These gravimetric values comprise JEFFCAT  Z-110 catalyzer and are used as any other amine catalyst of active catalyst.In addition, other known tertiary amine catalyst, its organic carboxylate and can be used as cocatalyst as the organo-tin compound of promotor usually.
Weight with 100 parts of polyvalent alcohols is benchmark, and the amount of the trimer catalyst that exists in composition is 0.02 to 10 weight part, and more preferably 0.1 to 5 weight part wherein can prepare foams according to the present invention by described composition.Applied " trimer catalyst " is meant and can promotes the isocyanate functional group to be converted into any catalyzer of trimer structure in this specification sheets and appended claim, concerning those skilled in the art, this trimeric structure is known as isocyanuric acid ester.Trimer catalyst comprises an alkali metal salt of carboxylic acid, as sodium, potassium, lithium or cesium salt.In the forming process of isocyanate trimer, three-NCO group reacts the formation isocyanurate structure each other.Typical trimer catalyst comprises potassium octanoate and potassium acetate.In addition, some amine also can be used as trimer catalyst, wherein part comprises: the JEFFCAT  TR-52 that is obtained by Texas Austin's Huntsman Petrochemical Corporation, and by Air Products and Chemicals, the TMR  that Inc obtains, TMR2 , TMR3.
The preparation temperature of foam product of the present invention can be the arbitrary temp between about 25 ℃ to about 200 ℃.The preparation pressure of foam product of the present invention can be any pressure of about 1 pound per square inch (" psi ") between about 3000psi.
Preparing in the method for foam product according to the present invention and trimer catalyst applied in any combination JEFFCAT  Z-110, can use polyvalent alcohol, polymeric polyisocyanate and foaming agent, stablizer, and other known auxiliary agent if desired, comprise flame retardance, but be not limited to this.
Though provide and described the present invention with reference to some preferred embodiment, those of skill in the art clearly of the present invention can do the change and the modification of equivalence after reading and having understood this specification sheets and appended claim.The present invention includes all such modifications and change, and limit the present invention by the scope of following claim.

Claims (20)

1. a catalyzer that is used for being formed by isocyanic ester and polyvalent alcohol polyisocyanurate foam comprises
A) comprise N, N, the amine component of N '-trimethylammonium amino ethyl ethanolamine; With
B) trimer catalyst component.
2. claim 1 catalyzer, wherein said trimer catalyst comprises an alkali metal salt of carboxylic acid.
3. claim 2 catalyzer, wherein said salt is selected from: the sad and acetate that is selected from the element of lithium, sodium, potassium and caesium.
4. claim 1 catalyzer further comprises additional amine component.
5. claim 4 catalyzer, wherein said additional amine component is selected from: five methyl diethylentriamine, dimethylcyclohexylam,ne, 2,2 '-two (N of oxygen, N-dimethyl ethane amine), amino-phenol, dimethylethanolamine, lupetazin, N-ethylmorpholine, N-methylmorpholine, 1,3,5-triazines-1,3,5 (2H, 4H, 6H)-three propane amine, N, N, N ', N ', N ", N " hexamethyl, 1, the 3-propanediamine, N '-(3-(dimethylamino) propyl group)-N, the N-dimethyl, the 2-propyl alcohol, 1-(two (3-dimethylamino) propyl group) amino), 2-((2-(2-(dimethylamino) oxyethyl group) ethyl) methylamino)-ethanol, dimethylamino ethoxy ethanol, 1, the 3-propanediamine, N-[3-(dimethylamino) propyl group]-N, N ', N '-trimethylammonium, 1, the 3-propanediamine, N, two [3-(dimethylamino) the propyl group]-N ' of N-, N '-dimethyl, morpholine, 4,4 '-(oxygen two-2,1-ethane two bases) two dimorpholino ethane and triethylenediamine.
6. the catalyzer of claim 1 further includes machine tin compound.
7. a method for preparing the isocyanuric acid ester foam product comprises the steps:
A) provide isocyanic ester and polyvalent alcohol;
B) provide catalyzer, described catalyzer comprises:
I) comprise N, N, the amine component of N '-trimethylammonium amino ethyl ethanolamine; With
Ii) trimer catalyst component; With
C) described isocyanic ester is contacted with described polyvalent alcohol.
8. the method for claim 7, wherein said isocyanic ester is selected from aromatics di-isocyanate, polymeric isocyanic ester, aliphatic di-isocyanate and aliphatic tri-isocyanate.
9. the method for claim 7, wherein said polyvalent alcohol is selected from aromatic polyester polyvalent alcohol, amino polyol, Man Xini polyvalent alcohol, sucrose deutero-polyvalent alcohol, sorbyl alcohol deutero-polyvalent alcohol and composition thereof.
10. the method for claim 7, wherein said trimer catalyst is selected from potassium octanoate, potassium acetate, JEFFCAT  TR-52,2 ethyl hexanoic acid 2-hydroxypropyl trimethyl ammonium and formic acid 2-hydroxypropyl trimethyl ammonium.
11. the method for claim 7, wherein said catalyzer further comprises:
Iii) be selected from the second following amine component: five methyl diethylentriamine, dimethylethanolamine, 2,2 '-oxygen two (N, N-dimethyl ethane amine), triethylenediamines, 1,3,5-triazine-1,3,5 (2H, 4H, 6H)-three propane amine, N, N, N ', N ', N ", N " hexamethyl, 1,3-propanediamine, N, two [3-(dimethylamino) the propyl group]-N ' of N-, N '-dimethyl, amino-phenol, 1,3-propanediamine and N-[3-(dimethylamino) propyl group]-N, N ', N '-trimethylammonium.
12. a method for preparing the isocyanuric acid ester foam product comprises the steps:
A) provide isocyanic ester and polyvalent alcohol;
B) provide whipping agent;
C) provide catalyzer, described catalyzer comprises:
I) comprise N, N, the amine component of N '-trimethylammonium amino ethyl ethanolamine; With
Ii) trimer catalyst component;
D) in the presence of described catalyzer and described whipping agent, isocyanic ester is contacted with polyvalent alcohol.
13. the method for claim 12, wherein said isocyanic ester are selected from aromatics di-isocyanate, polymeric isocyanic ester, aliphatic di-isocyanate and aliphatic tri-isocyanate.
14. the method for claim 12, wherein said polyvalent alcohol are selected from aromatic polyester polyvalent alcohol, amino polyol, Man Xini polyvalent alcohol, sucrose deutero-polyvalent alcohol, sorbyl alcohol deutero-polyvalent alcohol and composition thereof.
15. the method for claim 12, wherein said trimer catalyst are selected from 2 ethyl hexanoic acid 2-hydroxypropyl trimethyl ammonium and formic acid 2-hydroxypropyl trimethyl ammonium.
16. the method for claim 12, wherein said whipping agent are selected from water, carbonic acid gas, pentane, iso-pentane, pentamethylene, butane, R-141b  and R-245FA .
17. the method for claim 12, wherein said catalyzer further comprises:
Iii) be selected from the second following amine component: five methyl diethylentriamine, dimethylethanolamine, 2,2 '-oxygen two (N, N-dimethyl ethane amine), triethylenediamines, 1,3,5-triazine-1,3,5 (2H, 4H, 6H)-three propane amine, N, N, N ', N ', N ", N " hexamethyl, 1,3-propanediamine, N, two [3-(dimethylamino) the propyl group]-N ' of N-, N '-dimethyl, amino-phenol, 1,3-propanediamine and N-[3-(dimethylamino) propyl group]-N, N ', N '-trimethylammonium.
18. comprise N, N, the polyisocyanurate foam of N '-trimethylammonium amino ethyl ethanolamine.
19. comprise N, N, the polyisocyanurate foam of N '-trimethylammonium amino ethyl ethanolamine and trimer catalyst.
20. the foams of claim 18, wherein said trimer catalyst is selected from potassium octanoate and potassium acetate.
CNA028293312A 2002-07-18 2002-07-18 Catalyst combination for increasing trimer content in foam Pending CN1639240A (en)

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CN1899693B (en) * 2005-07-21 2012-01-25 赢创高施米特有限公司 Trimerization catalysts
CN101501092B (en) * 2006-08-11 2011-09-28 东曹株式会社 Catalyst composition for polyurethane resin production and method for producing polyurethane resin
CN102432813A (en) * 2011-03-21 2012-05-02 常州凯诺深冷科技工程有限公司 Method for preparing PIR (polyisocyanurate) material with ionic liquid catalyst
CN113286836A (en) * 2019-01-22 2021-08-20 科思创知识产权两合公司 Composite materials based on dual cure urethane and isocyanurate polymers
CN113286836B (en) * 2019-01-22 2024-02-13 科思创知识产权两合公司 Composite materials based on dual-cured urethane and isocyanurate polymers

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AU2002346113A1 (en) 2004-02-09
WO2004009687A1 (en) 2004-01-29

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