CN100503690C - Double-component catalyst for cyanate solidification reaction and its preparing process - Google Patents
Double-component catalyst for cyanate solidification reaction and its preparing process Download PDFInfo
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- CN100503690C CN100503690C CNB2005101122505A CN200510112250A CN100503690C CN 100503690 C CN100503690 C CN 100503690C CN B2005101122505 A CNB2005101122505 A CN B2005101122505A CN 200510112250 A CN200510112250 A CN 200510112250A CN 100503690 C CN100503690 C CN 100503690C
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- cyanate
- tin compound
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- compound
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Abstract
The invention discloses a bi-component organic tin compound catalyst and making method, which is applied to fix cyanate resin, wherein the catalyst consists of organic tin compound and reacting micromolecular compound; the molecular formula of organic tin compound is (H9C4)2Sn(NCO-R-OCN)2, which displays active diluent to form polymer at solidifying time of cyanate resin; two components are stirred under 40-80 deg. c for 15-25min, which are cooled to indoor temperature.
Description
Technical field
The invention belongs to chemical field, relate to catalyzer, be particularly useful for the catalyzer of the curing reaction of cyanate ester resin.
Background technology
Cyanate ester resin is a kind of thermosetting resin, has good heat-resistant, mechanical property, dielectric properties and moisture-proof thermal stability etc.As the matrix resin of preparation performance resins based composites, cyanate and matrix material thereof can be used as structured material, electromagnetic wave transparent material, adhesives, dielectric function material etc. and are applied to fields such as aerospace field, electronic information.
Yet simple cyanate is difficult to the thermofixation moulding, is not both having under the situation of extra catalyst, and its thermofixation reaction is slow and difficult.Therefore, be easy to the thermofixation moulding, must in resin system, add catalyzer to promote its curing reaction in order to make cyanate ester resin.
At present known compound that can catalysis cyanate thermofixation reaction mainly contains following a few class: compound catalyst (as phenol, amine, imidazoles etc.), transition metal salt/nonyl phenol mixed catalyst, UV-light activated catalyst and the organo-tin compound catalyzer etc. that contain reactive hydrogen.Find that in actual applications catalyzer has bigger influence to cyanate cured resin and performance of composites thereof.
Though contain the thermofixation reaction that the compound of reactive hydrogen can the catalysis cyanate, its large usage quantity can also generate the imines class by product of poor heat resistance with the cyanate ester monomer reaction, has reduced the heat-resistant stability of cured resin, does not generally use separately.
At US 4,608, in 434, the hybrid catalyst system of having reported transition metal salt (octylate of zinc, tin, copper, cobalt etc., naphthenate, acetylacetonate etc.) and nonyl phenol has advantages of high catalytic activity to the curing reaction of cyanate.The hydrotropy effect of transition metal salt is played in the adding of nonyl phenol on the one hand, and it still is a promotor on the other hand.But the catalytic selectivity of this class catalyzer is poor, transition metal salt is in the curing reaction while of catalysis cyanate, pyrolysis and hydrolysis reaction that can catalysis paracyanogen acid esters under higher temperature can cause adverse influence to cyanate cured resin and performance of composites thereof.
At US 5,215, in 860, reported that a class has the active organic transition metal composition catalyst of UV-light.It mainly is cyclopentadiene metallic carbonyls title complex, it at first mixes the reaction that cyanate functional group substituted carbonyl takes place in the back under ultraviolet light irradiation with cyanate ester monomer, and generate the catalyst activity component, use the curing reaction of this catalyst activity catalytic cyanate again.This class catalyzer has catalytic activity and selectivity preferably, but the influence of its catalytic activity and preparation process is bigger, promptly is subjected to the intensity of ultraviolet light irradiation, the difference of time, and catalytic activity changes greatly, and level of response is difficult to control.Simultaneously, cyclopentadiene metallic carbonyls title complex costs an arm and a leg, and also is unfavorable for applying of it.
A kind of organo-tin compound catalyzer (H
9C
4)
2Sn (NCO-R-OCN)
2, it can by price suitably, the commercialization reagent that is easy to obtain is through the prepared in reaction of simple controllable, has advantages of high catalytic activity and selectivity, simultaneously, it and cyanate ester monomer have good compatibility, do not need to add solubility promoter or stablizer etc.Its feature structure can be expressed as:
(H
9C
4)
2Sn (NCO-R-OCN)
2(NCO-R-OCN is a cyanate ester monomer, and the R group depends on the structure of the cyanate ester monomer that is adopted)
This component can be by document (Wenfeng Li, Guozheng Liang, Wenli Xin, Trizane Reactionof Cyanate Ester Resin Systems Catalyzed by Organic Tin Compound:Kinetics andMechanism, Polymer International, 2004, the method preparation of 53:869-876) being introduced.The raw material that is adopted is dibutyl tin laurate (DBTDL) and cyanate ester monomer (as bisphenol A cyanate ester, bis-phenol L type cyanate etc.), the primary process of its preparation is: take by weighing DBTDL and cyanate ester monomer by 1:2 (mol), at 60~80 ℃ of reaction 20~30min, promptly make the organo-tin compound catalyzer.
Yet,, be about every 1g cyanate ester monomer and need add organotin catalysts [Sn] 50~500*10 because the consumption of this organotin catalysts is very little
-6G, wayward its add-on makes to be restricted in actual use.
Summary of the invention
The purpose of this invention is to provide a kind of two-pack organotin catalysts that is applicable to the ethylene rhodanate resin curing reaction.It has advantages of high catalytic activity and selectivity, and simultaneously, it can dissolve well and be distributed in the cyanate ester monomer.
Another object of the present invention provides a kind of preparation method who is applicable to the two-pack organotin catalysts of ethylene rhodanate resin curing reaction.
For achieving the above object, the technical solution used in the present invention is:
A kind of bicomponent catalyst that can be used for the cyanate curing reaction contains organo-tin compound and active small molecular compound.
Further, the molecular formula of this organo-tin compound is: (H
9C
4)
2Sn (NCO-R-OCN)
2
This micromolecular compound can autohemagglutination or form superpolymer with the cyanate copolymerization in the cyanate ester monomer curing reaction.
This micromolecular compound is liquid Resins, epoxy or vinyl compound.
The concentration of this organo-tin compound in catalyzer is 1~5% weight.
The concentration of this micromolecular compound in catalyzer is 99~95% weight.
Its consumption when the curing reaction of catalysis cyanate is 2~5% weight.
Organo-tin compound catalyzer and active small molecular compound heated and stirred 15~25 minutes under 40~80 ℃ condition.
The composition of two-pack organo-tin compound catalyzer comprises two components of A and B:
The A component is an organo-tin compound, and molecular formula is:
(H
9C
4)
2Sn(NCO-R-OCN)
2
Wherein, R is the substituting group that contains phenyl ring, and concrete structure depends on the structure of the cyanate ester monomer that is adopted, and is generally dihydroxyphenyl propane (diphenyl propane) type that is easy to obtain or bis-phenol L (diphenylethane) type etc.
The B component is reactive micromolecular compound, comprises epoxy, vinyl compound etc.The selection principle of B component is to be fluent meterial under room temperature state, can dissolve the A component, and self also can be dissolved in the cyanate ester monomer, and himself can form high polymer by polyreaction under heated condition.
Can be used as the Resins, epoxy that the B component is used, as: E-51 Resins, epoxy, TDE-85 Resins, epoxy etc.
Can be used as the vinyl compound that the B component is used, as: vinylbenzene, Vinylstyrene, diallyl phthalate, properties of diallyl isophathalate etc.
B component itself not with A component generation chemical reaction, it is to add as the thinner of A component, its purpose is to make the A component to be easy to accurate weighing.Chemical reaction also can take place and generate high molecular polymer, thereby be referred to as reactive thinner in the present invention in the thermofixation reaction process of cyanate ester monomer in the B component.Can generate polyether structure by ring-opening polymerization as epoxy, perhaps with polyisocyanate reactant Sheng oxazoline ketone structure, vinyl compound can generate the linear macromolecule polymkeric substance by radical polymerization.Like this, behind the cyanate completion of cure, do not have micromolecular compound in the system, the mechanics of cured product, performance such as heat-resisting will can not be affected.
1g need add [Sn]=50~500*10 by the catalysis cyanate ester monomer
-6G calculates the quality of A component, and the calculating formula of [Sn] is
Wherein M is the molecular weight of organo-tin compound, the difference of the cyanate ester monomer that is adopted during according to preparation, and the M value is different; 118.7 be the nucleidic mass of Sn, W
AQuality for the A component.
Need add the 5g bicomponent catalyst by catalysis cyanate ester monomer 100g and calculate, in bicomponent catalyst [Sn] ' concentration be:
The add-on of B component is calculated as follows:
W wherein
ABe the quality of A component, W
BQuality for the B component.
Component A (1~5% weight) and B component (95~99% weight) are stirred 15~25min under 40~80 ℃ heating condition, its dissolving is uniformly dispersed after, naturally cool to room temperature and promptly make two-pack organo-tin compound catalyzer.
Temperature, the preparation of time for bicomponent catalyst do not influence, as long as it is just passable to reach homodisperse.Equally, the mass ratio of component A and B component is only influential to the concentration of [Sn], finally shows as the difference of the quality of the bicomponent catalyst that adds in " application examples ".
The two-pack organotin catalysts that is applicable to the ethylene rhodanate resin curing reaction of the present invention has advantages of high catalytic activity and selectivity, can dissolve well to be distributed in the cyanate ester monomer, is easy to weighing simultaneously so that the control consumption.
Description of drawings
Fig. 1 is DSC (differential scanning calorimetry) curve of the DSC collection of illustrative plates (a) of cyanate ester resin for the cyanate ester monomer of adding two-pack organo-tin compound catalyzer, (b) is DSC (differential scanning calorimetry) curve that does not add the cyanate ester monomer of catalyzer.The curing reaction exothermic maximum peak of cyanate ester monomer is reduced to 209 ℃ by 290 ℃ behind the adding catalyzer, has reduced about 80 ℃, shows that catalyzer of the present invention has good catalytic activity.
Embodiment
The present invention adopts reactive micromolecular compound to dilute organo-tin compound as reactive thinner; make it be easier to accurately quantitative and weighing; simultaneously; micromolecular compound is along with the curing reaction of cyanate carries out; autohemagglutination or with the cyanate copolymerization; thereby make hybrid catalyst system in the performance katalysis, can not reduce the performance (in high performance cyanate, introduce second communicate regular meeting make reductions such as resistance toheat, mechanical property, dielectric properties) of cyanate ester polymer again.Therefore, need not consider the size of its molecular weight, only calculate its quality (, for example can get 5g) for weighing and convenience of calculation as the B component of reactive thinner.The temperature that adopts during preparation (40~80 ℃) just is dispersed with machine tin compound for dissolving, to the not influence of its performance.As when adopting vinyl compound (being exactly low viscous liquid under the room temperature), temperature will be hanged down (40~60 ℃), and when adopting epoxy (viscosity is big), temperature will higher (60~80 ℃).
The preparation of organo-tin compound (bisphenol A-type):
Take by weighing 11.4g dibutyl tin laurate (DBTDL, 0.018mol) and the 10.0g bisphenol A cyanate ester (BADCy, 0.036mol) in beaker, 60~80 ℃ the reaction 20~30min, promptly make the organo-tin compound catalyzer, [Sn]=0.1g in every 1g organo-tin compound.
The preparation of organo-tin compound (bis-phenol L type):
Take by weighing 10.1g dibutyl tin laurate (DBTDL, 0.016mol) and 8.5g 4,4 '-two cyanate ester based-diphenyl propane (BEDCy, 0.036mol) in beaker, at 40~70 ℃ of reaction 20~30min, promptly make the organo-tin compound catalyzer, [Sn]=0.1g in every 1g organo-tin compound.
Embodiment 1:
Take by weighing 268g epoxy E-51 resin and place beaker, in oil bath, be heated to 60~80 ℃, add 10.7g organo-tin compound (bisphenol A-type), continue to keep 60~80 ℃ of temperature, and stirring 15min, stop heating, naturally cool to room temperature, obtain sundown thick liquid nano two-pack organo-tin compound catalyzer.Tin content [Sn]=0.003845g in every 1g bicomponent catalyst.
Embodiment 2:
Except that epoxy E-51 resin takes by weighing the 536g, other is identical with embodiment 1.Tin content [Sn]=0.001922g in every 1g bicomponent catalyst.
Embodiment 3:
Take by weighing the 245g properties of diallyl isophathalate and place beaker, in oil bath, be heated to 40~60 ℃, add 5.5g organo-tin compound (bis-phenol L type), continue to keep 40~60 ℃ of temperature, and stirring 15min, stop heating, naturally cool to room temperature, obtain the liquid two-pack organo-tin compound of sundown low viscosity catalyzer.Tin content [Sn]=0.00221g in every 1g bicomponent catalyst.
Application examples:
Take by weighing 100g bisphenol A cyanate ester monomer and place beaker, in 100 ℃ of oil baths, be heated to fusion, adding is by the two-pack organo-tin compound catalyzer 5g of embodiment 1 preparation, after stirring, pour in the glass mold of anticipating vacuum outgas 10min into, put into the electronics baking oven then, technology by 180 ℃/1h+200 ℃/2h is solidified, and at last at 220 ℃ of after fixing 2h, obtains the cyanate cured resin of organotin catalytic curing.Second-order transition temperature (Tg) with DMA method test cured resin is 276 ℃.
Claims (2)
1, a kind of bicomponent catalyst that is used for the cyanate curing reaction is characterized in that: be made up of organo-tin compound and reactive thinner;
The molecular formula of this organo-tin compound is: (H
9C
4)
2Sn (NCO-R-OCN)
2, wherein, R is the substituting group that contains phenyl ring, the described substituting group that contains phenyl ring is bisphenol A-type or bis-phenol L type;
This reactive thinner is liquid Resins, epoxy or vinyl compound, and it can autohemagglutination or form superpolymer with the cyanate copolymerization in the cyanate ester monomer curing reaction;
The concentration of this organo-tin compound in catalyzer is 1~5% weight.
2, the described using method that is used for the bicomponent catalyst of cyanate curing reaction of claim 1 is characterized in that: its consumption when the curing reaction of catalysis cyanate is 2~5% weight.
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CN100503690C true CN100503690C (en) | 2009-06-24 |
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CN102286151B (en) * | 2011-06-29 | 2012-12-05 | 同济大学 | Thermosetting modified cyanate ester resin and preparation method thereof |
CN102336892A (en) * | 2011-06-29 | 2012-02-01 | 同济大学 | Modified cyanate ester resin system for package substrate, and preparation method and application thereof |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1040211A (en) * | 1984-10-05 | 1990-03-07 | 通用电气公司 | Low viscosity epoxy resin compositions |
CN1467244A (en) * | 2003-03-07 | 2004-01-14 | 梁国正 | Organic tin compound for cyanate ester resin curing reaction and method for preparing the same |
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2005
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1040211A (en) * | 1984-10-05 | 1990-03-07 | 通用电气公司 | Low viscosity epoxy resin compositions |
CN1467244A (en) * | 2003-03-07 | 2004-01-14 | 梁国正 | Organic tin compound for cyanate ester resin curing reaction and method for preparing the same |
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