CN100554313C - The preparation method of aryl ethane and cyanate resin copolymer - Google Patents
The preparation method of aryl ethane and cyanate resin copolymer Download PDFInfo
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- CN100554313C CN100554313C CNB2007100436307A CN200710043630A CN100554313C CN 100554313 C CN100554313 C CN 100554313C CN B2007100436307 A CNB2007100436307 A CN B2007100436307A CN 200710043630 A CN200710043630 A CN 200710043630A CN 100554313 C CN100554313 C CN 100554313C
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Abstract
The preparation method of aryl ethane of the present invention and cyanate multipolymer by containing the cross-linked polymer that triazine ring, phenyl ring or nitrogenous fragrant heterocycle are formed, belongs to a class performance resins in its chemical structure.It is to carry out the cyclisation copolyreaction by aryl ethane and cyanate under catalyst action to get.The present invention's design and the multipolymer of preparing have high thermal stability, low-k and dielectric loss, and good mechanical performance.
Description
Technical field
The present invention relates to aryl ethane and cyanate resin copolymer, be used for high numeral and high frequency printed circuit board (PCB), coating, tackiness agent, electromagnetic wave transparent material and the space flight and aviation performance of high performance structures composite matrix resin and the performance of poly-aryl ethane based composites to improve cyanate ester resin, refer in particular to the preparation method of aryl ethane and cyanate resin copolymer.
Background technology
Cyanate ester resin is meant the compound that contains two or more cyanato-functional groups, and the trimerization annulation takes place under the effect of heat or catalyzer for it, forms the triazine ring cross-linked network structure.The dielectric properties of the cyanate ester resin tool excellence after the curing, high glass transition temperature, low rate of moisture absorption, little thermal expansivity, excellent mechanical property and adhesive property.(HAMERTON I.Chemistry and technology of cyanateesters[M] .Chapman and Hall:Glasgow, Blackie Academic﹠amp; Professional, 1994) its over-all properties is better than high-performance epoxy resin (EP) and bimaleimide resin (BMI), obtains extensive must the application in fields such as mechanical structure spare, electromagnetic wave transparent material, matrix material and high-frequency circuit board manufacturings in recent years.(FANGT, SHIMP D A.Polycyanate esters:science and applications[J] .Prog.Polym.Sci., 1995 (20): 61-118) poly-aryl ethane resin is meant a resinoid matrix that contains phenyl ring and two or more ethynyls in molecular structure, can obtain cured article by trimerization cyclopolymerization between monomer.Because it is the highly cross-linked aromatics phenyl polymer of a kind of only carbon elements and protium, theoretical charring rate is up to 90%.The poly-topmost advantage of aryl ethane is that second-order transition temperature is high, the ablation favorable reproducibility, and the mechanical behavior under high temperature conservation rate is good.(Katzman H A., Ployarylacetylene-matrix composites for solidrocket motor components, Advanced Materials, 1995,26 (3), yet 21-27), though discover carbon/poly-aryl ethane matrix material carbon forming rate, ablation resistance is much better than carbon/phenolic composite of using so far really, but the deadly defect that exists is that the many benzene ring structures that gather aryl ethane cause that matrix fragility is bigger at present, adhesive property is poor, and the matrix material interlayer cutting performance of poly-aryl ethane and carbon cloth wetting property difference band is poor, further uses thereby influence it to a certain extent.And, also have some weakness for cyanate ester resin, and promptly toughness is relatively poor, and thermotolerance is not ideal enough.If can improve resistance toheat largely, then will enlarge its range of application biglyyer.How to make this two classes performance resins both keep original premium properties, can improve its deficiency again, become a great problem in this investigation of materials field.
Summary of the invention
The present invention is just in order to overcome above-mentioned deficiency, a kind of preparation method of aryl ethane and cyanate resin copolymer of simple modification by copolymerization is provided, improved the over-all properties of cyanate ester resin and aryl ethane matrix resin, improve its application performance as circuit card, tackiness agent, coating, electromagnetic wave transparent material and matrix material, main innovation is that carrying out modification by copolymerization with aryl ethane and cyanate ester resin obtains, and specifically implements like this:
Aryl ethane and cyanate resin copolymer, in its chemical structure by containing the cross-linked polymer that phenyl ring or nitrogenous fragrant heterocycle are formed.Its preparation method: with aryl ethane and cyanate ester monomer is raw material, transition metal organometallic compound is a catalyzer, after cyanate ester monomer is heated to liquid state, stir and add aryl ethane, the mass ratio of aryl ethane and cyanate is 0.1-10, even in 80-110 ℃ of fusion, add catalyzer transition metal organometallic compound and triphenylphosphine again in the every gram resin of 20-500ppm/, front and back two constituent masses are than being 0.2-5, after catalyzer dissolved fully, at 120-180 ℃ of polymerization 6-10 hour, 210-250 ℃ was continued polymerization 6-8 hour, finish polymerization, obtain aryl ethane and cyanate resin copolymer.
Cyanate among the present invention can be the cyanate of different backbone structures, comprises bisphenol A-type, bisphenol E-type, Bisphenol F type, bis-phenol L type, bis-phenol M type, phenol aldehyde type etc.
Aryl ethane among the present invention can be a diacetylene aromatic hydrocarbons, comprises diacetylene-benzene, a diacetylene-benzene, diacetylene biphenyl, diacetylene ditan etc.; Also can be polyacetylene base aromatic hydrocarbons, comprise three ethynyl triphenyl methanes and three ethynyl triphenylbenzenes.
In the preparation of multipolymer of the present invention, transition metal organometallic compound as catalyzer can be acetyl acetone salt (as acetylacetonate nickel, acetylacetone cobalt, acetylacetone copper etc.) or naphthenate etc., the catalyzer add-on is the every gram resin of 150-300ppm/ preferably, transition metal organometallic compound is 0.2-5 with triphenylphosphine two constituent masses ratio, is preferably 0.5-2.
The type of heating that the present invention adopts can be oil bath heating, electronics baking oven or infrared radiation heating.
The present invention can obtain to have high thermal stability thus, low-k and dielectric loss, and the aryl ethane and the cyanate resin copolymer of good mechanical performance.Compare with pure cyanate ester resin, the matrix resin second-order transition temperature that is made of this multipolymer significantly improves, and Young's modulus increases, and specific inductivity and dielectric loss obviously reduce; Compare with pure aryl ethane, the adhesive property of gained multipolymer improves greatly.
Embodiment:
Embodiment 1:
In being furnished with the container of stirring, add bisphenol A cyanate ester resin 69g, the oil bath heating is treated to begin to stir after the bisphenol A cyanate ester resin fusion, in 100 ℃ of addings to diacetylene-benzene 6.9g, after treating dissolving evenly, add 300ppm/ every gram resin catalyst acetylacetonate nickel and triphenylphosphine (1: 1), treat that catalyzer dissolves fully, polymerization is 9 hours in 140 ℃ of Electric heat ovens, continue polymerase 17s hour in 220 ℃ again, finish polymerization, obtain multipolymer.
Embodiment 2:
In being furnished with the container of stirring, add bisphenol E-type cyanate resin 48g, infrared radiation heating is treated to begin to stir after the bisphenol E-type cyanate resin fusion, diacetylene-benzene 48g between 80 ℃ of addings, after treating dissolving evenly, add 250ppm/ every gram resin catalyst acetylacetone copper and triphenylphosphine (1: 5), treat that catalyzer dissolves fully, polymerase 17 hour in 170 ℃ of Electric heat ovens, in 210 ℃ of continuation polymerizations 8 hours, finish polymerization again, obtain multipolymer.
Embodiment 3:
In being furnished with the container of stirring, add Bisphenol F type cyanate ester resin 57g, oil bath heating is treated to begin to stir after the fusion of Bisphenol F type cyanate ester resin, adds diacetylene biphenyl 285g in 90 ℃, treat dissolving evenly after, add 150ppm/ every gram resin catalyst manganese acetylacetonate and triphenylphosphine (1: 2), treat that catalyzer dissolves fully, polymerization is 6 hours in 180 ℃ of Electric heat ovens, continues polymerization 6 hours in 240 ℃ again, finish polymerization, obtain multipolymer.
Embodiment 4:
In being furnished with the container of stirring, add bis-phenol L type cyanate ester resin 40g, the oil bath heating is treated to begin to stir after the fusion of bis-phenol L type cyanate ester resin, add three ethynyl triphenyl methane 400g in 110 ℃, after treating dissolving evenly, add 500ppm/ every gram resin catalyst acetylacetone cobalt and triphenylphosphine (1: 0.5), treat that catalyzer dissolves fully, in 160 ℃ of ir radiation polymerizations 8 hours, continue polymerase 17s hour in 250 ℃ again, finish polymerization, obtain multipolymer.
Embodiment 5:
In being furnished with the container of stirring, add phenol aldehyde type cyanate ester resin 50g, the oil bath heating is treated to begin to stir after the fusion of phenol aldehyde type cyanate ester resin, add three ethynyl triphenylbenzene 100g in 100 ℃, after treating dissolving evenly, add 20ppm/ every gram resin catalyst cobalt naphthenate and triphenylphosphine (1: 0.2), treat that catalyzer dissolves fully, polymerization is 10 hours in 120 ℃ of Electric heat ovens, in 230 ℃ of continuation polymerizations 6 hours, finish polymerization again, obtain multipolymer.
Claims (6)
1. the preparation method of aryl ethane and cyanate resin copolymer, it is characterized in that with aryl ethane and cyanate ester monomer be raw material, transition metal organometallic compound is a catalyzer, after cyanate ester monomer is heated to liquid state, stir and add aryl ethane, the mass ratio of aryl ethane and cyanate is 0.1-10, even in 80-110 ℃ of fusion, add catalyzer transition metal organometallic compound and triphenylphosphine again in the every gram resin of 20-500ppm/, front and back two constituent masses are than being 0.2-5, after catalyzer dissolves fully, at 120-180 ℃ of polymerization 6-10 hour, 210-250 ℃ was continued polymerization 6-8 hour, finishing polymerization, obtain multipolymer, is by containing phenyl ring in the multipolymer chemical structure, or the cross-linked polymer of nitrogenous fragrant heterocycle composition, wherein said cyanate is the cyanate of different backbone structures, i.e. bisphenol A-type, bisphenol E-type, the Bisphenol F type, bis-phenol L type, bis-phenol M type, phenol aldehyde type.
2. the preparation method of aryl ethane according to claim 1 and cyanate resin copolymer, it is characterized in that aryl ethane is a diacetylene aromatic hydrocarbons, diacetylene aromatic hydrocarbons is meant diacetylene-benzene, a diacetylene-benzene, diacetylene biphenyl, diacetylene ditan; Also can be polyacetylene base aromatic hydrocarbons, polyacetylene base aromatic hydrocarbons be meant three ethynyl triphenyl methanes, three ethynyl triphenylbenzenes.
3. the preparation method of aryl ethane according to claim 1 and cyanate resin copolymer, it is characterized in that the transition metal organometallic compound as catalyzer is acetyl acetone salt or naphthenate, acetyl acetone salt is meant manganese acetylacetonate, acetylacetone cobalt, acetylacetone copper.
4. the preparation method of aryl ethane according to claim 1 and cyanate resin copolymer is characterized in that the mass ratio of transition metal organometallic compound and triphenylphosphine two components is 0.5-2 in the catalyzer.
5. the preparation method of aryl ethane according to claim 1 and cyanate resin copolymer is characterized in that the catalyzer add-on is the every gram resin of a 150-300ppm/ meter.
6. the preparation method of aryl ethane according to claim 1 and cyanate resin copolymer, when it is characterized in that aryl ethane and cyanate ester resin blend with oil bath heating or electronics baking oven or infrared radiation heating.
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| CN101864076A (en) * | 2010-05-14 | 2010-10-20 | 华东理工大学 | Cyanate resin modified by phenylacetylene base silane resin and preparation method thereof |
| CN106281202A (en) * | 2016-08-11 | 2017-01-04 | 安徽龙川橡塑科技有限公司 | A kind of binding agent for polyurethane screen and using method |
| CN111269569B (en) * | 2018-12-04 | 2023-04-07 | 洛阳尖端技术研究院 | Polyaryne resin modified cyanate ester resin and preparation method thereof |
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Assignee: Jiangsu Tian-zhu Chemical Technology Co., Ltd. Assignor: East China University of Science and Technology Contract record no.: 2010320000754 Denomination of invention: Aryl radical acetylene and cyanate resin copolymer preparation method Granted publication date: 20091028 License type: Exclusive License Open date: 20080206 Record date: 20100621 |
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