JPH01182318A - Arylcyclobutane/dienophyl copolymer - Google Patents

Abstract

PURPOSE: To obtain a copolymer comprising a monomer containing polymeric aryl cyclobutane and a monomer containing polymeric dienophil, which is excellent in adhesion, thermal stability and solvent resistance, and suitable for adhesive and coating material.

CONSTITUTION: This copolymer is obtained by polymerizing a monomer (preferably poly(styrene-co-4-vinyl benzocyclobutane) containing at least 2 kinds of polymeric arylcyclobutane (preferably benzocyclobutane), and a monomer (preferably 4,4'-diphenylether bismaleic imide) containing at least 2 kinds of polymeric diphenophil (preferably maleic imide), with a preferable ratio of maleic imide containing monomer to benzocyclobutane containing monomer of more than 1.

COPYRIGHT: (C)1989,JPO

Description

[Detailed Description of the Invention] The present invention provides arylcyclotutanko? RIMER COMPOSITION.

Arylcyclobutane resin consists of monomer, oligomer,
It is a group of Gle I limers and primers. Poly(arylcyclobutane)4rimer is disclosed in U.S. Patent No. 4.540.
, No. 763.

This remer is made by heating a resin having two or more arylcyclobutane components to a temperature sufficient to cleave the cyclobutane rings. The cleaved nine-cyclotane molecules react with each other to form a crosslinked polymer.

This 4-(arylcyclobutane)/rimer exhibits excellent thermal and oxidative stability. paints, adhesives,
It may also be used as a composite material. However, U.S. Pat.
．． No. s4o, 7si discloses that only 7-arylcyclobutane-containing monomer colors are prepared.

Because of the excellent properties exhibited by the arylcyclobutane component, it is desirable to have methods and compounds for making copolymer compositions of arylcyclobutane monomers and other monomers.

The invention relates to a monomer comprising at least 2s polymerizable cyclobutane component in polymeric form and at least 2'
This is a 4-lima composition comprising a 7-lime containing a polymerizable genophile component of m.

The mixture of genophile and cycloptane monomers provides a reactive heptamer system useful in the preparation of copolymer compositions.

Compared to homopolymer compositions made from either monomer, the 3-copolymer compositions have improved properties such as adhesion, thermal stability, solvent resistance, and dielectric constant. The copolymer compositions of the present invention may be either thermoplastic or thermoset polymer compositions and may be used in conventional thermoplastic or thermoset applications. Examples of such uses include adhesives, obstetrics, composite materials, etc.

The arylcyclobutane monomers of the present invention include monomers having at least 2 Jlfl polymerizable cyclobutane moieties, polymeric polymers, and oligomeric chains. The arylcyclobutane component is polymerizable when addition polymerization sites are provided under ring-cleavage conditions. Suitable arylcyclobutane monomers, gle I rimers and olipmers and their preparation are disclosed in US Pat. No. 4,540,763.

The method for producing the arylcyclobutane precursor is described in U.S. Pat.
．． No. 562.280 and No. 4,570,011.

Preferably, the arylcyclobutane monomer is a benzocyclobutane monomer of the formula:

(wherein R represents a polyvalent organic or inorganic component, or a direct bond).

A particularly preferred monomer is the reaction product of styrene and 4-vinylbenzocyclobutane. To form such a monomer, t-S is contacted with styrene t-4-vinylbenzocyclobutane in the presence of a suitable free radical initiator such as azobisisobutyronitrile. styrene and 4
- The vinylbenzocyclobutane compound is stoichiometric enough to provide 2m of polymerizable benzocyclobutane component.

This monomer is called d/s(styrene-co-4-vinylbeyzocyclobutane) and has the following formula.

Below margin (In the above formula, n and m represent an integer of at least 1) It is expressed as

A preferred benzocyclobutane monomer having an R group containing an aromatic ring is 4. in the presence of triethylamine and dilated methylene. Eisoglobilidenediphenol (bisphenol A) JjJl-4-benzocyclobutane-
4-Produced by contacting with carboxylic acid. Bisphenol A and benzocyclobutane compounds are 2
The stoichiometry is sufficient to provide a polymerizable benzocyclobutane component of the plant, and the R group is of the following formula.

Hereinafter, it is expressed by a colloid (in the above formula, X represents an integer of at least 1).

Preferred benzocyclobutane monomers with RlIg containing an amino group include: 1. l-cal is prepared by contacting a diamino-alkane with 4-benzocyclobutanecarginic acid in the presence of sildiimidazole.

The diamino-alkane and pentcyclobutane compounds are stoichiometric enough to provide 2:4 benzocyclobutane components, and the R group is of the formula:

Below margin (In the above formula, n and X represent at least l integers) It is expressed as

Preferred benzocyclobutane monomers with RIIsf: containing unsaturated hydrocarbon groups are prepared by contacting divinylbenzene monomer with 4-bromobenzocyclobutane in the presence of a suitable/porous catalyst. This divinylbenzene and benzocyclobutane compound is
The stoichiometry is sufficient to provide two polymerizable benzocyclobutane components, and the R group is of the following formula.

The following is represented by a blank space (in the above formula, X represents an integer of at least 1).

A preferred benzocyclobutane monomer having an R group containing a siloxane group is a benzocyclobutane monomer having an R group containing siloxane groups.
．． 1.3.Produced by contacting 3-tetramethyl-1,3-divinyl dichloromethane with 4-bromobenzocyclobutane, the divinyl dichloromethane and benzocyclobutane compound contains two polymerizable benzocyclobutane components. and the R group is of the formula:

The following is represented by a blank space (in the above formula, X represents an integer of at least l).

Many other penzocyclobutane monomers that may be used as monomers in the present invention include U.S. Pat.
No. 763.

The arylcyclobutane monomer may be a heterocyclic arylcyclobutane monomer. A preferred heterocyclic arylcyclobutane monomer is cyclobutapyridine heptamer, which has the following formula.

(In the above formula, R represents the one defined above.)

A method for producing cyclobutapyridine and substituted cyclobutapyridine is described in Riemann and Trachanopus - (J,
M., Rlemann and W., Traha.
novsScy) Tstrmh@dron L@tt
@rs, No. 22, pp. 1867-1870, (197
7 years), (cyclobuta (b) pyridine and cyclobuta (,) pyridine; and Crow, Kano and / 肂va” (W-D, Crow.

A.N.Khan and M.N.Paddoa
-Row)'s Au5tralian Jourt+a
l of Ch@m1stry *No. 28, 1741
~1754 pages, (1975).

(2-Methylcyclovine [b]pyridine). Suitable methods for preparing other substituted cyclobutapyridines are given in the references below. 0r(an
lc Rsaction 3 Volume 1, page 91 (2-aminocyclobuta(b)viridiy): B@rlchta
.

No. 57, pages 791 and 1802, (1924
year), (2-hydroxycyclobuta(b) viridiy is 2
- aminocyclo ivy (b) produced from pyridine);
Hating@ran
d Li*bsn) Chemische, No. 48
No. 6.

p. 71, (1931), (2-chlorocyclobuta [b
] Pyridine Fi2-Hydroxycyclobuta (b) produced from pyridine).

Substituted heterocyclic arylcyclobutane compounds may be used to prepare heterocyclic arylcyclobutane heptamers. For example, maleamic acid derivatives of cyclobutapyridine are prepared by contacting with 2-abanocyclobutapyridyl maleic anhydride in the presence of a suitable organic solvent such as chloroform at a suitable reaction temperature. . Approximately equal moles or more of 2-aminocyclobutapyridine to maleic anhydride is used. Cyclobutapyridine maleate acid conductor in a suitable organic solvent.

For example, by treating the maleamide derivative in sodium acetate in acetic acid at a suitable reaction temperature,
2-(N--P reimidococyclobutapyridine may also be used. A suitable reaction temperature is 100-12
It is in the range of 0°C.

In other examples, 2-10 modiclotutaviridin is
It may also be used to produce vinylcyclobutapyridine. The bromocyclobutapyridine is contacted with excess ethylene in the presence of a suitable catalyst system and solvent, and at a suitable reaction temperature and under a suitable pressure. A suitable catalyst system includes t-acetate-yaradium(II), and a suitable co-catalyst is tri-o-)lylphosphine. Suitable solvents include acetonitrile and suitable reaction temperatures are 125°C. 2-vinylcyclobutapyridine may be contacted with styrene in the presence of a free radical initiator to obtain a vinyl crosslinked Isu (cyclo ivy pyridine).

In yet another example, a submerged, 2-f lomocyclobutapyridine may be used to produce a monocyclobutapyridine monomer with a vinyl bridge member that couples the cyclobutapyridine moiety with an organic molecular group such as an aromatic moiety. . For example, to produce 1-(4-methyl-phenyl)-2-(2-cyclobutapyridyl)ethane, an amount of 2-bromocyclobutapyridine is added in the presence of a suitable catalyst system.
Contact with slightly more molar fraction of 4-methylstyrene in a suitable solvent at suitable reaction conditions.

A suitable catalyst system is radium(n) acetate,
A suitable co-catalyst is trilotrylphosphine.

A suitable solvent is acetonitrile, and suitable reaction conditions are reflux for a sufficient period of time.

The genophile component is a component that reacts with the condensed diene to form a 6-membered ring. such ingredients.

Morrison and Gate (Morrison and B.
oyd). Suitable components are alkenyl components, preferably unsaturated hydrocarbon components having electron-withdrawing groups on adjacent carbons. Suitable electron-withdrawing groups are oxygen, nitrogen, halogen, phosphorus, and the like. Particularly preferred genophile components are asb-unsaturated car-nyl compounds, and the most preferred components are maleamide components.

A particularly preferred monomer is a monomer containing a polymerizable dienophile component that polymerizes near the temperature at which the cyclobutane-containing monomer polymerizes (ie, within 50°C). The most preferred monomer is the maleimide component t
-Including tr. The maleimide-containing monomer is heated to approximately 200°C.
Polymerizes with Such a monomer has the following formula.

It is represented by OO (in the above formula, X represents a polyvalent organic component and the symbol represents an inorganic component).

A preferred X group is represented by the following formula %formula%() (In the above formula, n represents at least l).

The manufacturing method of such maleimide is Polym@r
s Vol. 26, p. 1561, September 1985.

Still other preferred Genophile components are alkaline components, particularly acetylene components.

The amount of arylcyclobutane-containing ester and genophile monomers used in the preparation of the co/lima monomers of the present invention varies. The cyclobutane monomer is used at more than 100 cents by weight of the monomer mixture, and the genophile monomer is used at more than 100 cents by weight of the monomer mixture. Preferably, if the genophile monomer is polymerized at a temperature lower than the polymerization temperature of the arylcyclobutane monomer, the genophile monomer relative to the amount of arylcyclobutane monomer! - The ratio of amounts is 1 or more.

In addition to the arylcyclobutane monomers and genophile monomers, the copolymer compositions of the present invention comprise other monomers or zy-cr-compositions that can polymerize independently and provide a permeating network or copolymerize with the monomers. . Suitable desired monomer or polymer compositions include monoarylcyclobutane monomers (i.e., monoarylcyclobutane monomers containing only one 7lylcyclobutane component).
) and other poly(arylcyclobutane) mono! −(
That is, a monomer containing at least two arylcyclobutane components) t-contains. A preferred monoarylcyclobutane is an A,B-monomer having a polymerizable benzocyclobutane component and a reactive maleimide component. Such a seven-pointer is the formula below.

(In the above formula, R' represents a direct bond or a polyvalent organic or inorganic component, and may be the same as or different from R.) Such A,B monomers are prepared by dehydrogenation of benzocyclobutenylmaleamidic acid. Maleamic acid derivatives and methods for their preparation are disclosed in US Pat. No. 4,638,078.

The copolymer composition may also contain desired components determined by the particular application of the cotetramer. Such desired ingredients include: fiber fillers such as glass, quartz and graphite fibers; organic and inorganic powder fillers; catalysts:
Contains hardening agent: female fuel agent: etc. For example, the copolymer composition may include an amount of a conductive metal, such as gold or silver powder, and may be used as a die bond material. In other examples, the copolymer composition may include an amount of mono-reinforced glass fibers and may be used as a composite material.

The copolymer composition combines arylcyclobutane monomers and genophile monomers to form a mixture;
It is produced by treating a monomer mixture with under sufficient polymerization conditions. Since this monomer mixture is thermally polymerized, application of heat is the preferred polymerization step.

To prepare the most preferred copolymer of benzocyclobutane monomer and bismaleimide monomer,
A suitable polymerization temperature is the temperature at which the cyclobutane ring cleaves to give the dientaig structure. Preferably the temperature is about 180<0>C to 270<0>C.

Ideally, it may contain a unit of the co/IJ mer tf of benzocyclobutane and bismaleimide monomers represented by the following formula (in which R and X represent the above definitions).

Preparation of the copolymers of the present invention improves the physical properties of homopolymers made from this monomer.

For example, adhesive/thermal stability, solvent resistance, dielectric constant, elongation at break (toughness) 1, etc. are improved. Surprisingly, the hot wet strength of this maleimide polymer also increases.

The following examples are references only and are examples of the present invention! Jt - non-limiting.

A mixture of the two components of this system was first prepared. The mixture was supplied with a nitrogen atmosphere from a 1 g oil/water apparatus with a gas inlet tube, magnetic stirrer, and stopper.
Manufactured in a round bottom flask from 00go. here 10
0 mj of dichloromethane and 25.9 Isu(styrene-co-4-bi-rubenzocyclobutane) (5) 4-vinylbenzocyclobutane% 1.25II 4
-Vinylbenzocyclobutane, MW-130,29,0
,0096 equivalents) were added. This mixture was stirred until completely dissolved. Add 4.4' of 3.45N to this mixture.
-diphenyl ether bismaleimide (+1flW
-360,0,00958 mol) and 1501114
of dichloromethane was added. This mixture was stirred until completely dissolved.

The yellow solution was poured into a cake pan lined with a Teflon sheet and the dichloromethane was allowed to evaporate in a fume hood overnight. Obtained. The bright yellow illimer sheet was cut into small pieces with scissors and these pieces were ground using a Willie mill. This ground polymer was dried in an open vacuum overnight (
0.1 min Hg.

(100℃) Make sure to dry. The dry powder was 19.7.9%, giving a recovery rate of 69/cent. Differential scanning calorimetry showed a glass transition at 86°C, and a temperature of 259.8°C.
The main polymerization exotherm, which is the peak, was shown.

Apply a suitable mold release agent to a piece of thick aluminum foil,
Place the coated surface facing up on a flat steel plate. On top of this was placed a steel plate with a hole cut in the shape of a standard tensile test rod. This equipment was sprayed with a gold mold release agent.

The benzocyclobutane/bismaleimide mixture was placed in the mold form and the copolymer was pressed in with a foam 4 tier.

Further, a copolymer was placed on top of this, and then another release agent-treated aluminum foil and another steel plate were covered. This device was heated to 210° C. and placed in a hydraulic press, and the press plate was closed until it touched both plates. The mold was then held for 10 minutes while the copolymer melted and was pressurized to 15 ton ram pressure. The mold was then heated to 255° C. for eIO minutes. This mold t-250℃~255℃ for another 10 minutes.
I kept it. At completion, the pressure was released and the mold apparatus was transferred from hot pressure to cold pressure where the mold was allowed to cool for 110 minutes. If you take out a part of this four-wheeler.

The appearance was yellowish brown and the weight was 6.7 g.

A copolymer containing 9.6 mmol of benzocyclobutane and 9.6 mmol of bismaleinimide t- exhibits a glass transition of 86° C. before polymerization. This sample completely disintegrated in methylene chloride, while it was obtained by thermal copolymerization of bismaleimide and polystyrene-co-4-vinylbenzocyclobutane: 2/rimer swells but dissolves or It won't collapse.

7.5 cents per mole of benzocyclobutane of polystyrene containing vinylbenzocyclobutane 4-
A mixture of vinylbenzocyclobutane and 1 mole of bismaleimide provides a copolymer with a glass transition of 108 DEG C. to 111 DEG C. before curing.

Curing of this material by heating to 300°C.

Co/having a glass transition temperature of 114°C to 121'C
Rimmer? Yo JJ. Another Sunnol is prepared in a mixture containing 5 percent benzocyclobutane and 3.85 mmol bismaleimide and crosslinked by heating to 320°C. The uncured material exhibits a glass transition temperature of 89°C, while after curing this glass transition temperature is 110°C.
Move to. Polystyrene mixed with bismaleimide
All samples of Boo-4-vinylbenzocyclobutane.

The polymerization exotherm starts at 190°C to 200°C and peaks at 250°C to 260°C.

Below margin

Claims (1)

Claims: 1. A copolymer composition comprising a monomer containing at least two polymerizable arylcyclobutane components in polymeric form and a monomer containing at least two polymerizable dienophile components. 2. The copolymer composition according to claim 1, wherein the arylcyclobutane component is a benzocyclobutane component. 3. The copolymer composition according to claim 2, wherein the dienophile component is an alkenyl component. 4. The copolymer composition according to claim 2, wherein the dienophile component is an α,β-unsaturated carbonyl component. 5. The copolymer composition according to claim 2, wherein the dienophile component is a maleimide component. 6. The copolymer composition according to claim 5, wherein the ratio of the amount of maleimide-containing monomer to benzocyclobutane-containing monomer is 1 or more. 7. The monomer containing at least two kinds of polymerizable arylcyclobutane components is poly(styrene-co-4-vinylbenzocyclobutane), and the monomer containing at least two kinds of polymerizable dienophile components is 4,4'-diphenyl ether bismalein. Claim 1, which is an imide
Copolymer compositions as described in .