CN1074312C - Composite catalyst for tripolymerization of isocyanic ester - Google Patents
Composite catalyst for tripolymerization of isocyanic esterInfo
- Publication number
- CN1074312C CN1074312C CN97119455A CN97119455A CN1074312C CN 1074312 C CN1074312 C CN 1074312C CN 97119455 A CN97119455 A CN 97119455A CN 97119455 A CN97119455 A CN 97119455A CN 1074312 C CN1074312 C CN 1074312C
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- CN
- China
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- reaction
- composite catalyst
- catalyst
- weight ratio
- tripolymerization
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Abstract
The present invention relates to a composite catalyst for the trimerization reaction of isocyanate, which is prepared from triethylenediamine and methylaminomethyl phenol, wherein the weight ratio of the triethylenediamine to the methylaminomethyl phenol is (1 to 0.5) to (1 to 2). The present invention has the advantages of simple and easy preparation, convenient operation and use, high conversion rate, high selectivity, etc., and is suitable for aliphatic polyisocyanate and aromatic polyisocyanate.
Description
The present invention relates to a kind of composite catalyst that is used for the isocyanate trimerization reaction.
The polymer that contains the isocyanuric acid ester hexa-member heterocycle on the main chain is commonly referred to as poly-isocyanurate (PIR).Isocyanurate ring is an organic preferably heteroatomic ring of hear resistance, owing to do not have unsettled H atom on the N atom, thereby heat decomposition temperature is very high.In recent years, successfully developed modification PIR resin for base heat-resisting hard bubbled, H level electrotechnical, electronic is already with envelope material and insulated paint and heat-resisting winding resin etc.Second characteristic of PIR are difficult combustion of its structure and low cigarette.For example the PIR of modification twines resin and not only has preferable heatproof, antiseptic property, and durable, flame retardancy matter outstanding, limited oxygen index (LOI) is 65.5%.In addition, the 3rd characteristics of PIR are that viscosity is lower, and can or solidify, thereby become the groundwork resin of contemporary state-of-the-art thermosetting resin process technology (SRIM) slightly under the high-temperature fast in room temperature.
Isocyanuric acid ester is to become cyclization to become by polyisocyanates self trimerization under catalyst action.Selection of catalysts is the key point of trimerization reaction, and selected catalyst should have excellent catalytic effect, easy control of reaction system, advantage such as easy to use, it should be noted that especially isocyanuric acid ester has very strong selectivity to catalyst.The result of catalytic reaction should make the conversion ratio height of trimerization reaction, and the product of HMW and dimer minimizing as far as possible in the product.It is more to can be used for this catalyst for reaction kind, generally includes: slaine, carboxylate, phosphorus-containing compound, Mannich alkali, phenols and amine etc.The independent use of these catalyst because lower, the reaction speed of catalytic efficiency is slow, the required reaction time is prolonged or required catalyst amount strengthens, thereby improves cost and handles for the back processing of reaction system and bring adverse effect.
The present invention gets compound catalyst for trimerization (A+B) by the mixed of two kinds of single catalyst A, B, and is used for the trimerization reaction of isocyanates.Since the synergy of composite catalyst, and catalyst active center is changed, form the zwitterionic activated centre-N of yin, yang
+-C-C-O
--or-N
+-C-C-N
--.This synergy has produced the unexistent good result of single catalyst, and reaction speed is accelerated, and selectivity improves.When reaction reaches the predetermined extent of reaction, in time add terminator cessation reaction with weight such as catalyst.
Composite catalyst of the present invention consists of (weight ratio):
Triethylene diamine: many methylaminos methylphenol=1: 0.5～1: 2
Aforesaid many methylaminos methylphenol can replace with epoxides such as glycidol benzyl ethyl ethers.
Composite catalyst best group of the present invention becomes (weight ratio):
Triethylene diamine: many methylaminos methylphenol=1: 1
Processing method of the present invention is that above-mentioned composite catalyst is added in the isocyanate solution that is dissolved in mixed solvent (methyl+dimethyl formamide) in proportion, under stirring, keep 50 ℃ of reaction temperatures, sampling regularly is with di-n-butylamine Equivalent method analysis-NCO content.Terminators such as the chlorobenzoyl chloride of weight such as final adding of reaction and catalyst or p-methyl benzenesulfonic acid finish reaction.Obtain the purpose product.
The present invention has the following advantages:
1. simple, the easy row of this composite catalyst preparation is easy to use.
2. compare with single catalyst, composite catalyst has higher conversion ratio and selectivity preferably.
3. replace single catalyst with composite catalyst, reaction speed is accelerated, save the reaction time, or under same reaction speed, make catalyst amount few, reduced the cost of course of reaction.
Composite catalyst of the present invention is applicable to all aliphatic polyisocyantes and aromatic polyisocyanate.
Embodiment one
At one agitator is housed, temperature is taken into account in the reactor of reflux condensate device, add 2,4-methyl vulcabond (TDI-100) 100g, mixed solvent (weight ratio is 1: the 1) 50g that adds toluene and dimethyl formamide (DMF) by 50% of its weight, heat temperature raising to 50 ℃ under stirring, drip 0.2g triethylene diamine+0.2gDMP-30 composite catalyst (weight ratio 1: 1), keep 50 ℃ of reaction temperatures, sampling is regularly analyzed residual NCO-NCO content with the di-n-butylamine Equivalent method.Drip the chlorobenzoyl chloride cessation reaction of 0.4g at last.The rate constant that records this system is 5.08, and the half-life is 15.0min.
Embodiment two
At one agitator is housed, temperature is taken into account in the reactor of reflux condensate device, add 4,4-toluene di-isocyanate(TDI) (MDI) 80g, mixed solvent (weight ratio is 1: the 1) 40g that adds toluene and dimethyl formamide (DMF) by 50% of its weight, heat temperature raising to 50 ℃ under stirring, drip 0.2g triethylene diamine+0.1g glycidol benzyl ethyl ether composite catalyst (weight ratio 1: 0.5), keep 50 ℃ of reaction temperatures, sampling regularly is listed as the NCO-NCO content that stays with the analysis of di-n-butylamine Equivalent method.Drip the chlorobenzoyl chloride cessation reaction of 0.3g at last.The rate constant that records this system is 10.10, and the half-life is 6.5min.
Embodiment three
At one agitator is housed, temperature is taken into account in the reactor of reflux condensate device, add 4,4-methyl diphenylene diisocyanate (MDI) 80g, mixed solvent (weight ratio is 1: the 1) 40g that adds toluene and dimethyl formamide (DMF) by 50% of its weight, heat temperature raising to 50 ℃ under stirring, drip 0.1g triethylene diamine+0.2gDMP-30 composite catalyst (weight ratio is 1: 2), keep 50 ℃ of reaction temperatures, sampling is regularly analyzed residual NCO-NCO content with the di-n-butylamine Equivalent method.Drip the p-methyl benzenesulfonic acid cessation reaction of 0.3g at last.The rate constant that records this system is 7.72, and the half-life is 8.5min.
Comparative Examples one
With the composite catalyst in the 0.4DMP-30 single catalyst alternate embodiment one, other reaction condition is identical with embodiment one.The rate constant that records this system is 3.05, and the half-life is 25.0min.
Comparative Examples two
With the composite catalyst in the 0.4 triethylene diamine single catalyst alternate embodiment one, other reaction condition is identical with embodiment one.The rate constant that records this system is 2.54, and the half-life is 30.0min.
Comparative Examples three
With the composite catalyst in the 0.3g triethylene diamine single catalyst alternate embodiment two, other reaction condition is identical with embodiment two.The rate constant that records this system is 3.36, and the half-life is 19.5min.
Comparative Examples four
With the composite catalyst in the 0.3gDMP-30 single catalyst alternate embodiment three, other reaction condition is identical with embodiment three.The rate constant that records this system is 5.24, and the half-life is 12.5min.
Claims (2)
1. one kind is used for the composite catalyst that isocyanate trimerization reacts, and it is characterized in that weight ratio consists of: triethylene diamine: many methylaminos methylphenol or glycidol benzyl ethyl ether epoxide=and 1: 0.5～1: 2.
2. composite catalyst according to claim 1 is characterized in that weight ratio consists of: triethylene diamine: many methylaminos methylphenol or glycidol benzyl ethyl ether epoxide=and 1: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97119455A CN1074312C (en) | 1997-11-04 | 1997-11-04 | Composite catalyst for tripolymerization of isocyanic ester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97119455A CN1074312C (en) | 1997-11-04 | 1997-11-04 | Composite catalyst for tripolymerization of isocyanic ester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1216263A CN1216263A (en) | 1999-05-12 |
| CN1074312C true CN1074312C (en) | 2001-11-07 |
Family
ID=5175386
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97119455A Expired - Fee Related CN1074312C (en) | 1997-11-04 | 1997-11-04 | Composite catalyst for tripolymerization of isocyanic ester |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1074312C (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102069012A (en) * | 2011-01-11 | 2011-05-25 | 山西大学 | Catalyst for catalyzing trimerization of isocyanate to synthesize isocyanurate |
| CN102911343B (en) * | 2012-10-24 | 2014-12-31 | 华南理工大学 | Preparation method of toluene diisocyanate trimer curing agent |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD219029A3 (en) * | 1982-07-23 | 1985-02-20 | Univ Dresden Tech | PROCESS FOR POLYMERIZING ORGANIC ISOCYANATES |
| SU1219592A1 (en) * | 1983-09-14 | 1986-03-23 | Московский ордена Ленина и ордена Трудового Красного Знамени химико-технологический институт им.Д.И.Менделеева | Method of producing low-temperature cooling oligourethanmethacrylatisocyanurate |
| DD236745A1 (en) * | 1984-04-11 | 1986-06-18 | Univ Dresden Tech | PROCESS FOR POLYMERIZING ISOCYANATES (IV) |
| JPH026480A (en) * | 1988-06-24 | 1990-01-10 | Sumitomo Bayer Urethane Kk | Production of isocyanurate group-containing polyisocyanate |
-
1997
- 1997-11-04 CN CN97119455A patent/CN1074312C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD219029A3 (en) * | 1982-07-23 | 1985-02-20 | Univ Dresden Tech | PROCESS FOR POLYMERIZING ORGANIC ISOCYANATES |
| SU1219592A1 (en) * | 1983-09-14 | 1986-03-23 | Московский ордена Ленина и ордена Трудового Красного Знамени химико-технологический институт им.Д.И.Менделеева | Method of producing low-temperature cooling oligourethanmethacrylatisocyanurate |
| DD236745A1 (en) * | 1984-04-11 | 1986-06-18 | Univ Dresden Tech | PROCESS FOR POLYMERIZING ISOCYANATES (IV) |
| JPH026480A (en) * | 1988-06-24 | 1990-01-10 | Sumitomo Bayer Urethane Kk | Production of isocyanurate group-containing polyisocyanate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1216263A (en) | 1999-05-12 |
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