JPS63161004A - Prepolymer from aromatic dicarboxylic acid diallyl ester - Google Patents

Abstract

PURPOSE:To provide the titled crosslinkable prepolymer, capable of giving cured products of water resistance, having on one side a side chain with its end carrying C=C double bond and on the other side, a side chain carrying perfluoroalkenyloxy chain. CONSTITUTION:The objective prepolymer containing pref. >=10wt.% of recurring units of formula I (X is 6-14C perfluoroalkenyl group), with an average molecu lar weight 3,000-10,000 and iodine value 25-80 in general. Recurring units other than that of the formula I are, e.g., of vinyl acetate, methacrylamide, maleic anhydride. This prepolymer can be obtained by either homopolymerization of a fluorine-contg. dicarboxylic acid diallyl ester or by copolymerization of said ester with copolymerizable component(s) such as ethyl ene and/or isoprene. Even the prepolymer containing >=50wt.% of the recurring units of the formula I has a water absorption rate of 1/10.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a novel diallyl aromatic dicarboxylic acid prepolymer.

(Prior Art) Diallyl aromatic nocarboxylate, for example diallyl phthalate, is a thermosetting resin monomer having two polymerizable functional groups. Generally, in order to obtain a polymer from a monomer having two or more polymerizable functional groups and mold it into a desired shape, the polymerization reaction must be stopped once at a degree of polymerization that is solvent soluble or thermoplastic. , after or simultaneously with molding as a solvent solution or as a thermoplastic resin,
Further polymerization is carried out to form an insoluble and infusible resin, that is, a cured product. The solvent-soluble or thermoplastic polymer used in this process is generally referred to as a prepolymer.

Conventional cured products of prepolymers such as diallyl phthalate are useful as molding materials for electrical parts such as sockets and connectors, laminates, decorative boards, etc., but they have the drawback of poor water resistance.

(Problems to be Solved by the Invention) An object of the present invention is to provide a novel diallyl aromatic dicarboxylic acid prepolymer that provides a cured product with excellent water resistance.

(Means for Solving the Problems) The present invention relates to a prepolymer of diallyl fluorine-containing aromatic dicarboxylic acid containing a repeating unit represented by the formula (representing a perfluoroalkenyl group of X11116-14).

The perfluoroalkenyl group having 6 to 14 carbon atoms represented by Represents a perfluoroalkyl group having 1 to 6 carbon atoms, R
4 represents a perfluoroalkyl group having 1 to 5 carbon atoms.)
Particularly preferred are groups formed by the elimination of one fluorine atom from a dimer or trimer of hexafluoropropene, or a tetramer to heptamer of tetrafluoroethylene. Examples of the structural formulas are as follows.

(cp,)2c=6c,Fs, C.F.

In the present invention, the repeating unit represented by formula (1) is
Since diallyl fluorine-containing dicarboxylate represented by (X is the same as above), which is a monomer of the prepolymer of the present invention, is converted, the compound represented by formula (2) is a compound represented by formula H2 and/or The prepolymers of the present invention include:
Although these repeating units may be present in small amounts compared to the repeating units of formula (1), the presence of these repeating units is not necessary in the prepolymer of the present invention.

The present invention also includes copolymers containing repeating units of formula (1) and repeating units other than formula (1).

Examples of repeating units other than formula (1) include ethylene,
Vinyl acetate, vinyl fluoride, vinyl chloride, acrylamide, methacrylamide, styrene, a-methylstyrene,
p-methylstyrene, furkyl ester of acrylic or methacrylic acid, benzyl 7-acrylate or methacrylate, vinyl alkyl ether, halogenated alkyl vinyl ether, vinyl alkyl ketone, cyclohexyl acrylate or methacrylate, maleic anhydride, butadiene, isoprene, chloroprene, phthalic acid Examples include repeating units produced by cleavage of double bonds in various compounds such as diallyl, diallyl isophthalate, diallyl terephthalate, and the like.

The preferred molecular weight of the prepolymer of the present invention is about 1,000 to 50,000 in number average molecular weight. Especially about 3000~1
0000, and a preferable iodine value (sample t
The number of grams of iodine added to OOg is preferably in the range of about 10-95, more preferably about 25-80.

If the molecular weight is too high, it will be difficult to process the deltized polymer; if the molecular weight is too small, it will be difficult to obtain a cured product with practical strength; and if the iodine value is too low, it will be difficult to process the polymer. A cured product cannot be obtained, and if the size is too large, the cured product will have poor impact resistance.

The prepolymer of the present invention can be obtained by homopolymerizing or copolymerizing the above compound (2).

As a copolymerization component, ethylene compounds such as ethylene,
Vinyl acetate, vinyl fluoride, vinyl chloride, acrylamide, methacrylamide, styrene, a-7 tylstyrene,
p-methylstyrene, alkyl esters of acrylic or methacrylic acid, benzyl acrylate or methacrylate, vinyl alkyl ethers, halogenated alkyl vinyl ethers, vinyl alkyl ketones, cyclohexyl acrylate or methacrylate, maleic anhydride, conjugated diene compounds such as butadiene, isoprene , chlorobrene, independent diene compounds such as diallyl phthalate, diallyl isophthalate, diallyl terephthalate and the like. The proportion of the repeating unit (1) in the prepolymer is preferably about 1% (by weight, the same applies hereinafter) or more, preferably about 10% or more.

Water resistance is not expected below about 1%.

The method and conditions of the polymerization reaction can be arbitrarily selected, and for example, various methods such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization can be used in radical polymerization, and cationic polymerization can be used in ionic polymerization. Compounds that generate free radicals are used as initiators for radical polymerization. Preferred radical initiators include peroxides such as benzoyl peroxide, tert'f-thyl perbenzoate, acetyl benzoyl peroxide, succinyl peroxide, diisopropyl peroxynocarbonate, ammonium persal 7ate, and azobisisobutyronitrile. 7 zonitrile, etc. Also, the formula as described in Japanese Patent Publication No. 35-16035 [Z is C1, OH or any group that can be converted into an OH group, R is lower alkyl (C1 to C4 ), Haku is θ~4, ■
A chain length regulator represented by θ~(4-m)) can also be used.0 To control the molecular weight and prevent gelation, the chain length regulator is preferably used in an amount of about 10 to 25% by weight based on the monomer.
The polymerization can be carried out by adjusting the amount of polymerization initiator, polymerization temperature, polymerization time, etc. The amount of the radical initiator used is selected from the range of 0.1 to 10% (by weight) based on the monomer. However, the range of the amount of the initiator to be used is not limited to the above, and is appropriately selected depending on factors such as the degree of polymerization of the target polymer, reaction time, and polymerization temperature. The polymerization temperature is between -80°C and +250°C, depending on the decomposition temperature of the initiator. Generally -40℃~+150℃
As the solvent that can be used in the solution polymerization, the temperature preferably ranges from 0.degree. These may be used alone or in combination of two or more. In addition, in the case of cationic polymerization, a polymerizable initiator such as boron trisulfide ethyl etherate or aluminum chloride is used to
Polymerization can be carried out in a solvent such as toluene or benzene at a temperature of 0°C.

Conventional methods may be used to recover the polymer from the reaction mixture; for example, the polymerization product may be recovered from methanol, diisopropyl ether, dimethyl ether, petroleum ether,
Only the polymer is precipitated in addition to a poor solvent such as n-hexane (in which the polymer does not dissolve). To purify the polymer, the polymer obtained as a precipitate is mixed with acetone, methyl ethyl ketone, ethyl acetate, nooxane, tetrahydrofuran, It is preferable to dissolve the polymer in a solvent such as ethane dichloride, 900% form, ffi carbon chloride, trichloroethylene, benzene, toluene, or the like, and then reprecipitate the polymer in addition to the above-mentioned poor solvent.

Compound (2), which is a monomer of the prepolymer of the present invention, is a new compound, for example, a hydroxyaromatic carboxylic acid derivative represented by the formula
It is obtained by reacting a perfluoroalkene represented by F (X represents a perfluoroalkenyl group of !1116-14).

The above compound (3) is a new compound, and can be produced by, for example, esterifying hydroxyphthalic acid with allyl alcohol in the presence of a catalyst. The reaction is usually preferably carried out using about 2 to 40 moles of allyl alcohol per 1 mole of hydroxyphthalic acid. Examples of the catalyst include concentrated sulfuric acid, para-toluenesulfonic acid, and boron trisulfide ethyl etherate. The reaction temperature is preferably about 50-2
00℃, reaction time can be determined as appropriate (generally about 30 minutes ~
The reaction time is preferably about 20 hours, and the reaction pressure is not particularly limited.

This reaction is preferably carried out in a solvent. The solvent is preferably one that is azeotropic with water and does not substantially form a solution when mixed with water, such as benzene, toluene, xylene, diallyl ether, etc. The produced compound (3) can be processed by known methods such as concentration, It can be purified by extraction, distillation, chromatography, etc., but it can also be reacted with a perfluoroalkene represented by XF in the next step without purification.

The perfluoroalkene represented by the formula (representing a perfluoroalkyl group); particularly preferred examples include 2fi forms and trimers of hexafluoropropene;
Tetrafluoroethylene tetra- to heptamers can be mentioned, and examples of the structural formulas are as follows.

(CF,)2C=CF(C,F,), The reaction is preferably carried out in a solvent in the presence of a base. Examples of the base include triethylamine, trimethylamine,
Amines such as tripropylamine, alkali metals or their hydroxides, etc., and aprotic polar solvents such as acetonitrile, dimethylformamide, and trimethylsulfoxide are preferably used as the solvent. The ratio of compound (3) and perfluoroalkene is usually about 1 to 10 moles of the latter per 1 mole of the former.The reaction temperature can be selected as appropriate, but it is preferably about θ to 40°C, especially about θ to 20°C. A range is preferred. The base is used in an amount of about 1 to 1 mole of compound (3).
It is preferable to use it in a range of 20 mol. Compound (2), which is the target product, can usually be separated and recovered by a known method used for the separation of a mixed organic compound system in which a solid is dissolved in a liquid. The precipitate can be collected and recovered by distilling it under reduced pressure.

(4) Among the compounds represented by XF in the formula, R”
Compounds represented by F and are included.

From these, each is generated.

More specifically, for example is generated.

Compound (2) can also be obtained, for example, by reacting a known aromatic nocarboxylic acid represented by the formula (x is the same as above) with allyl alcohol. Compound (5) is a known compound. The reaction is preferably carried out in a solvent. Preferably, the solvent is one that is azeotropic with water and substantially miscible with water, such as benzene, toluene, xylene, diallyl ether, and the like. The ratio of compound (5) to allyl alcohol is preferably about 2 to 10 moles of the latter per 1 mole of the former. The reaction temperature can be selected as appropriate, but it is approximately 50℃.
A range of -200<0>C, especially about 70-160<0>C is preferred.

Compound (2), which is the target product, can be usually separated and recovered by a known method used for separating an organic compound mixture system in which a solid is dissolved in a liquid, such as concentration, distillation, gas chromatography, etc. can.

The prepolymer of the present invention can be used alone or in combination with a prepolymer such as noallyl phthalate, diallyl isophthalate, diallyl terephthalate, etc., by heat or light in the presence of a thermal polymerization initiator, a photopolymerization initiator, etc. Alternatively, curing can be carried out using active energy rays such as electron beams and umma rays in the absence of an initiator. In the presence of an initiator, it is also possible to mix monomers such as diallyl phthalate, diallyl isophthalate, diallyl terephthalate, etc. as carriers for the initiator. The amount of monomer used is preferably up to about 90% by weight in the mixture.

Examples of thermal polymerization initiators include ketone peroxides such as methyl ethyl ketone peroxide and cyclohexanone peroxide, t-butyl perbenzoate, and t-butyl perbenzoate.
Perester 79 such as butyl peroxy-2-ethylhexoate, hydroperoxides such as L-butyl hydroperoxide and cumene hydroperoxide, and noarsilver oxides such as benzoyl peroxide, etc., and photopolymerization can be initiated. Examples of the agent include benzoin alkyl ethers such as 2,2-noethoxyacetophenone and 2,2-dimethoxy-2-phenylacetophenone, 7cetophenones such as noethoxyacetophenone, ketones such as benzo7e/one, Examples include thioxanthone such as 2-chlorothioxanthone.

The amount of initiator used is about o, oot to 20% by weight, preferably about 0.1 to 10% by weight, based on the prepolymer and carrier.

Regardless of heat, light, or active energy rays, the curing temperature ranges from room temperature to 250°C, preferably from room temperature to 180°C.

(Effects of the Invention) Since the prepolymer of the present invention has a side chain having a carbon-carbon double bond at the end, it has crosslinkability and provides a cured product, and also has perfluoroalkenyl as another side chain. Since the prepolymer of the present invention has an oxidized polymer, the cured product provided by the prepolymer of the present invention has excellent water resistance. That is, the prepolymer of the present invention provides a cured product with extremely superior water resistance compared to conventional prepolymers such as diallyl phthalate, and has a repeating unit represented by formula (1) of about 50% by weight. %
Even with the prepolymer contained, a cured product exhibiting a water absorption rate of about 1/10 is obtained.

(Example) Reference examples, working examples, and comparative examples will be described below.

Reference Example 1 0.2 mole of 5-hydroxyisophthalic acid was placed in a reaction vessel equipped with a stirrer, a cooling tube, and a thermometer, and 0.6 mole of allyl alcohol, 3001 g of toluene, and 1.3 g of sulfuric acid were added.

0.2 g of p-methoxy 7 ether was added and the mixture was heated to reflux. The distilled water was condensed in a cooling tube and separated from toluene, which was continuously returned to the reaction vessel. After 8 hours, heating was stopped and the mixture was allowed to cool.

The total amount of water distilled out at this point was 7-1.

After washing the reaction solution with saturated brine until the aqueous layer no longer showed acidity, toluene was distilled off under reduced pressure. This concentrated solution was distilled under reduced pressure to obtain 27 g (yield: 52%) of diallyl 5-hydroxyinphthalate.

b, p, 202-205°C, 15 mmHg 26 g of diallyl 5-hydroxyisophthalate thus obtained was dissolved in 90 ml of dimethylformamide, and 31. While stirring, 45 g of hexafluoropropene trimer was added dropwise over 10 minutes at room temperature, and stirring was continued. After 2 hours, the reaction solution was poured into a large amount of diluted hydrochloric acid, and the precipitated oil was separated, washed with water, and distilled under reduced pressure to obtain 41 g of diallyl 5-(perfluorononenyloxy)isophthalate (compound A) (yield 59). %) was obtained.

b@p, 150-b Reference Example 2 4-(perfluorononenyloxy)phthalic acid was prepared in the same manner as in Reference Example 1 except that 4-hydroxyphthalic acid was used instead of 5-hydroxyisophthalic acid in Reference Example 1. Diallyl (compound B) was obtained.

b, p, 160-b Reference Example 3 In place of the hexafluoropropene trimer in Reference Example 1, dimer 30. 39 g of diallyl 5-(perfluorohexenyloxy)isophthalate (compound C) was obtained in the same manner as in Reference Example 1 except that the reaction temperature with diallyl 5-hydroxyisophthalate was 0 to 4°C.

b@p, 128-131°C 15-SoHgReference Example 4 4-(Perfluoro Diallyl decenyloxy)phthalate (compound +11 kD) was obtained.

b, 9.165-b Example I C0OCI(zct("CI(2) Compound A (250g), diallyl terephthalate 250
g.

Benzoyl peroxide 7g 5 Dibutyltin Shirathuro 6
1. 250 g of water was placed in a reaction vessel equipped with a stirrer and a cooling tube and reacted at 85° C. for 5 hours. After the reaction, it was cooled to room temperature and 50 g of acetone was added. was added and left to stand. The organic layer was dropped into a large amount of methanol while stirring, and the resulting precipitate was filtered, washed with methanol, dried under reduced pressure, and ground to a white powder of 120. I got it. This material has an iodine value of 66, a polystyrene equivalent number average molecular weight Mn determined by gel permeation chromatography of 8.6X103, a weight average molecular weight 1h of 5.3X10', and a fluorine content of 18.
It was 5wt%.

Therefore, the white powder was a prepolymer in which the molar ratio of compound (A) and diallyl terephthalate was 1:4.3. 50 parts by weight of this prepolymer was dissolved in 50 parts by weight of diallyl terephthalate, 1 part by weight of benzoyl peroxide was added, and the mixture was cast at 90°C in a Petri dish with an inner diameter of 50°C.
The mixture was heated for 8 hours to produce a casting plate with a diameter of 50 mm and a thickness of 31 mm.

Example 2 Compound B as diallyl fluorine-containing aromatic nocarboxylic acid
102 g of a white powder was obtained in the same manner as in Example 1, except that (250 g) was used and the reaction time was changed to 4 hours.

The iodine value of this product is 70, the Mn is 7.3X10', the same is 4.4X104, and the fluorine content is 18.6wt.
%Met.

Therefore, the white powder was a prepolymer in which the molar ratio of compound (B) and diallyl terephthalate was 1:4.3. Furthermore, using this prepolymer, a casting plate was produced in the same manner as in Example 1.

Example 3 148 g of white powder was obtained in the same manner as in Example 2, except that 375 g of compound (B) and 125 g of diallyl terephthalate were used. The iodine value of this thing is 49
, Mn is 1. lX10', Xi- was 4,6X 10%, and the fluorine content was 31.4 wt%. Therefore, the above white powder has a molar ratio of compound (B) and diallyl terephthalate of 1.
:1.4. Furthermore, using this prepolymer, a casting plate was produced in the same manner as in Example 1.

Example 4 118 g of white powder was obtained in the same manner as in Example 1, except that 125 g of diallyl phthalate and 125 g of diallyl inphthalate were used instead of diallyl terephthalate in Example 1. The iodine value of this thing is 65.8n, which is 7.2X10
', 8ga is 4,2X10', and the fluorine content is 18.
It was 7wt%. Therefore, the above white powder is compound (A)
The prepolymer had a molar ratio of 1:4.3 and diallyl ester. Furthermore, using this prepolymer, a casting plate was produced in the same manner as in Example 1.

Example 5 121 g of white powder was obtained in the same manner as in Example 1 except that diallyl isophthalate was used instead of diallyl terephthalate. The iodine value of this substance is 72, I
VII is 5.6X 10', simple is 6. lXl0', and the fluorine content was 18.5 wt%. Therefore, the white powder was a prepolymer in which the molar ratio of compound (A) and diallyl isophthalate was 1:4.3. Furthermore, using this prepolymer, a casting plate was produced in the same manner as in Example 1.

Example 6 87 g of a homopolymerized prepolymer of compound (B) was obtained in the same manner as in Example 2 except that diallyl terephthalate was not used and the entire amount was used as compound (B). The iodine value of this product was 28, the iodine value was 2.4 x 103.8, and the fluorine content was 45.9%. 50 parts by weight of this prepolymer and compound (B) were uniformly mixed under heating, 2 parts by weight of benzoyl peroxide was added, and the mixture was heated at 90° C. for 8 hours to prepare a casting plate.

Example 7 Compound c (300g), diallyl terephthalate 200
g.

7 g of benzoyl peroxide, 6 g of dibutyltin silica
, White powder 10 was prepared in the same manner as in Example 1 using 250 g of water.
8g was obtained. This one has an iodine value of 71, simple n=9.2X
10 pieces, simple = 5.9X10', and the fluorine content is 1
It was 9.8 wt%. Therefore, the above white powder is a compound (
The prepolymer had a molar ratio of C) and diallyl terephthalate of 1:2.1. A casting plate was prepared in the same manner as in Example 1 by mixing 60 parts by weight of this prepolymer with 40 parts by weight of diallyl terephthalate and adding 2 parts by weight of benzoyl peroxide.

Example 8 Compound 5 where X is a tetrafluoroethylene pentamer
107 g of a homopolymerized prepolymer was obtained in the same manner as in Example 6, except that 00 g was used and the reaction time was 6 hours. The iodine value of this product was 26, the Mn was 3.2 x 10', the same was 6,7 x 10', and the fluorine content was 48.5%. 70 parts by weight of this prepolymer and 30 parts by weight of compound (D)
Parts by weight were uniformly mixed under heating, 2 parts by weight of benzoyl peroxide was added, and a casting plate was prepared in the same manner as in Example 1.

Comparative Example 1 Diallyl phthalate prepolymer [trade name Guiso Gutsubu A, manufactured by Osaka Soda Co., Ltd., Mn = 6,7X103, g change =
2.6X10', iodine value 61) was dissolved in 50 parts by weight of diallyl terephthalate, 2 parts by weight of benzoyl peroxide was added, and a casting plate was prepared in the same manner as in Example 1.

Comparative Example 2 Terephthal F! ! Diallyl-based polymer [trade name: Guprene, manufactured by Osaka Soda Co., Ltd., simple n = 7, 3 x 10, lock = 2
．． A casting plate was prepared in the same manner as in Comparative Example 1, except that 5×10′, iodine value 51] was used instead of Guiso Gup A.

Using the casting plates obtained in Examples and Comparative Examples, JIS K
-6911, the water absorption rate at 23°C was measured.

The results are shown in Table 1.

Chapter 1 Table

Claims (3)

[Claims] (1) Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) A preform of diallyl fluorine-containing aromatic dicarboxylate containing a repeating unit represented by (X represents a perfluoroalkenyl group having 6 to 14 carbon atoms) polymer. (2) The prepolymer according to claim 1, wherein the proportion of repeating units of formula (1) in the prepolymer is at least 1% by weight. (3) The repeating unit other than formula (1) is diallyl phthalate,
The prepolymer according to claim 1, which is a repeating unit produced by cleavage of the double bond of at least one allyl group selected from the group of diallyl isophthalate and diallyl terephthalate.