CN1216263A - Composite catalyst for tripolymerization of isocyanic ester - Google Patents
Composite catalyst for tripolymerization of isocyanic ester Download PDFInfo
- Publication number
- CN1216263A CN1216263A CN 97119455 CN97119455A CN1216263A CN 1216263 A CN1216263 A CN 1216263A CN 97119455 CN97119455 CN 97119455 CN 97119455 A CN97119455 A CN 97119455A CN 1216263 A CN1216263 A CN 1216263A
- Authority
- CN
- China
- Prior art keywords
- composite catalyst
- reaction
- catalyst
- weight ratio
- tripolymerization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Catalysts (AREA)
Abstract
The catalyst consists of trivinyl diamine and polymethylamino methylphenol in the weight ratio of 1 to 0.5-2. It is easy to prepare and has high transforming rate and high selectivity and it is suitable for the tripolymerization of all aliphatic and aromatic isocyanic esters.
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 (toluene+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-toluene di-isocyanate(TDI) (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 is regularly analyzed residual NCO-NCO content with the 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 0.4g 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 (3)
1. a composite catalyst that is used for the isocyanate trimerization reaction is characterized in that consisting of (weight ratio)
Triethylene diamine: many methylaminos methylphenol=1: 0.5~1: 2
2. composite catalyst according to claim 1 is characterized in that described many methylaminos sylvan can replace with epoxides such as glycidol benzyl ethyl ethers.
3. composite catalyst according to claim 1 and 2 is characterized in that best form (weight ratio) is:
Triethylene diamine: many methylaminos methylphenol=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 true CN1216263A (en) | 1999-05-12 |
CN1074312C 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) |
Cited By (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 |
CN102911343A (en) * | 2012-10-24 | 2013-02-06 | 华南理工大学 | Preparation method of toluene diisocyanate trimer curing agent |
Family Cites Families (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) |
JP2692864B2 (en) * | 1988-06-24 | 1997-12-17 | 住友バイエルウレタン株式会社 | Process for producing polyisocyanate containing isocyanurate group |
-
1997
- 1997-11-04 CN CN97119455A patent/CN1074312C/en not_active Expired - Fee Related
Cited By (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 |
CN102911343A (en) * | 2012-10-24 | 2013-02-06 | 华南理工大学 | Preparation method of toluene diisocyanate trimer curing agent |
Also Published As
Publication number | Publication date |
---|---|
CN1074312C (en) | 2001-11-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CA2093884A1 (en) | Polyisocyanates containing allophanate and isocyanurate groups, a process for their production from a mixture of diisocyanates and their use in two-component coating compositions | |
CA1262595A (en) | Catalyst systems for polyurethane compositions | |
CA2125237A1 (en) | Polyisocyanates containing allophanate and isocyanurate groups, a process for their production from cyclic diisocyanates and their use in two-component coating compositions | |
Houghton et al. | Mechanism of tin (IV)-catalysed urethane formation | |
GB1506373A (en) | Process for the production of polyisocyanates containing isocyanurate groups | |
WO2004078820B1 (en) | Preparation of isocyanurate group containing polyisocyanate mixtures | |
CA2203229A1 (en) | Polyurethane powder coating compositions which have a low stoving temperature | |
CA2023635A1 (en) | Solutions of isocyanurate polyisocyanates in coatings solvents and a process for their production | |
EP0116068B1 (en) | Modified polyisocyanurate foam and method of preparation | |
DE4441176A1 (en) | Polyisocyanates containing allophanate groups | |
GR3017883T3 (en) | Polyisocyanates containing ether and urethane groups, process for their preparation and their use. | |
KR840006906A (en) | Reactive Polymers for Skin Treatment | |
GB1287803A (en) | Process for the manufacture of crystalline polyurethane plastics products based on diisocyanates and linear polyesters | |
DE409199T1 (en) | HARD POLYURETHANE POLYISOCYANURATE FOAMS AND METHOD FOR THE PRODUCTION THEREOF. | |
DE4302697A1 (en) | Process for the production of organic carbodiimides and their use as plastic stabilizers | |
CN1074312C (en) | Composite catalyst for tripolymerization of isocyanic ester | |
EP0472063A2 (en) | Isocyanurate groups containing polyisocyanate mixtures, process for their preparation and their use in the preparation of polyurethane foams | |
IE39531L (en) | Preparation of isocyanurate polyisocyanate solutions having¹a reduced free diisocyanate content | |
CN100494243C (en) | Method for the production of prepolymers containing isocyanate groups | |
CA2411930C (en) | Use of catalysts for the preparation of aliphatic oligocarbonate polyols | |
CN100379786C (en) | Low residual monomer IPDI-PPG prepolymer | |
GB1233252A (en) | ||
RU2003105466A (en) | Compositions of diphenylmethanediisocyanate | |
JPS57198760A (en) | Quick-drying covering composition | |
CA2014516A1 (en) | Transparent, compact polyurethane casting compositions that are sterilizable with superheated steam, process for preparing same, and their use, particularly for medical-technical particles |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C06 | Publication | ||
PB01 | Publication | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
C19 | Lapse of patent right due to non-payment of the annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |