JPS62106059A - Novel diol bisunsaturated carboxylic acid ester - Google Patents

Abstract

NEW MATERIAL:A diol bisunsaturated carboxylic acid ester, having 2 polymerizble vinyl bonds in the molecule and expressed by formula I (at least one of R1 and R2 is ester residue having aromatic ring; when only one of R1 and R2 represents ester residue, the other is 2-8C alkyl or alkenyl or 3-12C cycloalkyl; R3 is -(CH2)n-, -(CH2CH2O)m-, -CH2CH2-, formula II or III, etc.; n is 2-10; m is 1-10]. EXAMPLE:Diethylene glycol bisphenylfumarate. USE:A crosslinking polyfunctional monomer useful for synthesizing heat-resistant resins having a crosslinked structure by hompolymerization and modification of heat resistance, etc., of vinyl polymers as a crosslinking agent by copoly merization with another vinyl monomer. PREPARATION:A maleic acid monoester and a diol are used to afford the aimed compound expressed by formula I.

Description

Detailed Description of the Invention <Industrial Application Field> The present invention relates to a novel diol bis-unsaturated carboxylic acid ester, and more specifically to a novel diol bis fumarate and diol having two polymerizable vinyl bonds in the molecule. Concerning bismarate.

<Prior art and problems> Conventionally, polyfunctional monomers containing two or more double bonds in the molecule have been used as monomers or crosslinking agents to improve the heat resistance, solvent resistance, mechanical properties, etc. of vinyl polymers. Used for improving strength, etc. Examples of such polyfunctional heptamers include diallyl phthalate, diallyl isophthalate, triallyl isocyanurate, ethylene dimethacrylate, butylene dimethacrylate, and the like.

However, the polyfunctional monomers that cause crosslinking reactions are often subject to many regulations during polymerization, and the comonomers that can be used are limited, especially when modification is carried out by copolymerization with other monomers. was there. For example, when an allyl group having a diallyl or triallyl group is used as a functional group, comonomers for copolymerization are limited to similar allyl monomers, vinyl chloride, vinyl acetate, methyl methacrylate, etc., and it is difficult to use styrene. Di (meta)
Acrylates are good for styrene, (meth)acrylate, etc., but difficult to use for vinyl chloride and vinyl acetate, and have drawbacks such as a significant decrease in copolymerization rate and a decrease in molecular weight depending on the comonomer.

<Objective of the Invention> The present invention allows a crosslinked structure to be easily formed in a polymer structure by radical polymerization.

The object of the present invention is to provide novel diol bis fumarate and diol bismate, which are crosslinkable polyfunctional monomers that can be copolymerized with any of the monomers such as styrene, vinyl chloride, and vinyl acetate.

According to the present invention, the following general formula (]) % formula % (1) (wherein R, R and 2 are the same or different groups, and R □, at least one of R2 represents an ester residue having an aromatic ring, and when only one of R and R7 represents an ester residue having an aromatic ring, the other is an alkyl group or alkenyl having 2 to 8 carbon atoms. group or a cycloalkyl group having 3 to 12 carbon atoms, R1 is (CHz)n-2(CHzCHz
O)m CH2CH2゜-(cx-■2cH(c■■
3) O)ffi-cH2cH(cH,)-CH.

10-0-0-2 ■ CI(3 CH.

-(CI(2CH2Cchicken-◎-C-◎-(○CH,CH
2) -Q CH.

or CH.

■ Indicates Q C11°. However, n, m, and Q are each 2≦n≦10゜1≦m
Represents an integer of ≦10, 1≦Q≦10. ) A diol bis-unsaturated carboxylic acid ester having two polymerizable vinyl bonds in the molecule is provided.

The present invention will be explained in more detail below.

The present invention provides diol bisfumarate or diol bismate represented by the above general formula (1).

R1 and R2 in the formula are the same or different groups, and R
,, at least one of R2 is an ester residue having an aromatic ring, such as a phenyl group, a benzyl group, or a halogen-substituted phenyl group.

Examples include a phenyl group substituted with an alkyl nucleus, a benzyl group substituted with a halogen nucleus, a benzyl group substituted with an alkyl nucleus, a phenethyl group, an α-naphthyl group, a β-naphthyl group, 2-phenoxyethyl, and a biphenyl group.

On the other hand, when only one of R, R2 represents an ester residue having an aromatic ring, the other represents an alkyl group or alkenyl group having 2 to 8 carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms. When the alkyl group or alkenyl group has 9 or more carbon atoms or the cycloalkyl group has 13 or more carbon atoms, polymerizability decreases. Further, n, m, and Q in R3 of the above formula (1) are respectively 2≦n≦10, 1≦m≦10, 1≦Q
Indicates an integer of ≦10, and when n, m, and Q are 11 or more,
Composition becomes difficult.

Examples of diol bis fumarate or diol bismate that can be preferably used in the present invention include ethylene glycol bisphenyl fumarate, ethylene glycol bisol 1-thalol phenyl fumarate, diethylene glycol bisbenzyl fumarate, and diethylene glycol bisparabrom. Benzyl fumarate, diethylene glycol bisallyl benzyl fumarate, dipropylene glycol bisisoprobyl benzyl fumarate, dipropylene glycol bisorthomethylphenyl fumarate, dipropylene glycol bisorthoglolbenzyl methallyl fumarate, bisphenol A bisphenyl fumarate, Bisphenol A biscyclohexylbenzyl fumarate, Bisphenol A diethylene glycol bisbenzyl fumarate, Bisphenol A di(diethylene glycol) bisbenzyl fumarate, Bisphenol A di(diethylene glycol) bis-orthochlorobenzyl fumarate, Bisphenol A dipropylene glycol bisnaphthyl fumarate. In contrast to the above-mentioned trans fumarate, examples include cis-malate compounds.

To synthesize diol bisfumarate or diol bismale-1 of the present invention, first, maleic acid monoester is treated with a chlorinating agent such as thionyl chloride, phosphorus trichloride, or phosphorus pentachloride, and a base such as pyridine or triethylamine is used as a catalyst. to synthesize fumaric acid monoester chloride 1 or maleic acid monoester chloride. Thereafter, it is synthesized by esterifying fumaric acid monoester chloride or maleic acid monoester chloride and a predetermined diol in the presence of a base such as pyridine or triethylamine. Further, it can also be obtained by heat treatment or dehydration and esterification of a maleic acid monoester and a predetermined diol in the presence of an acid catalyst.

By using the diol bis fumarate or diol bismate of the present invention, a polymer can be obtained by homopolymerization or copolymerization, but in this case, it is carried out by a radical polymerization method using a general radical polymerization initiator. The polymerization can be carried out by known techniques such as bulk polymerization, suspension polymerization, emulsion polymerization, and solution polymerization. In the polymerization or copolymerization, diisopropylperoxydicarbonate-1-, diethylhexylperoxydicarbonate, t-butylperoxypivalet I~ is used as a radical initiator.

isobutyryl peroxide, lauroyl peroxide,
This can be carried out using hensyl peroxide, azobisisobutyronitrile, azobisdimethylvaleronitrile, persulfates, persulfate-bisulfite systems, and the like. The radical initiator is used in an amount of 0.01 to 10 wt%, more preferably 0.1 to 5 wt%, based on the diol bis fumarate or diol bismarate of the present invention, or a mixture of them and a copolymerizable monomer. Polymerization temperature 30-10
It is desirable to carry out the reaction at a temperature in the range of 0°C for about 1 to 72 hours.

The copolymerizable vinyl monomers that can be copolymerized with diol bisfumarate or diol bismale-1 as used in the present invention include 1, for example, styrene, methyl nucleus-substituted styrene, halogen+j, 'IV; substituted styrene, and a-methyl. Styrene, divinylbenzene, acid-resistant vinyl, vinyl chloride, vinylidene chloride, butyl vinyl ether, ethyl vinyl ether,
Acrylamide, N, N-dimethylacrylamide <
, ethyl acrylate, methyl methacrylate, acriconi-1-helyl, imbutylene, 1,3-butadiene, diallyl phthalate, diallyl isophthalate, diethylene glycol bisallyl carbonate merine 1-acid ester, 1-riadylisocyanurate, and the like.

<Effects of the Invention> Diol bisfumarate or diol bismale-1 of the present invention is a crosslinkable monomer having two polymerizable vinyl bonds in the molecule, and if 7F is independently polymerized by a radical polymerization method, a crosslinked structure can be formed. It is possible to synthesize a heat-resistant resin that has the following properties, and if it is copolymerized with other vinyl monomers, it can be used as a crosslinking agent.
It can be used to modify the heat resistance, solvent resistance, mechanical strength Jσ, etc. of vinyl polymers. In addition, since the ester residue contains an aromatic ring, the material has high refraction! (It is also effective as a chestnut W agent for chemical use.)

<Examples> Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

Oka I Reference 1-2 To 1 rnol of maleic acid monophenyl ester and maleic acid monobenzyl ester, 1 mol of 1-reprocessed tylamine as a catalyst and 500 mQ of benzene as a solvent were added, and 1.2 mol of thionyl chloride was added dropwise in a water bath, and then By reacting at room temperature for 4 days, removing the hydrochloride and distilling off the benzene, fumaric acid monophenyl chloride and fumaric acid monobenzyl chloride were synthesized, respectively. Furthermore, each obtained fumaric acid chloride was mixed with diethylene glycol (0.4m).

1) and 300 mQ of pyridine-benzene (1:1) under a water bath, and the mixture was reacted at room temperature for 10 hours. Then, pyridine hydrochloride was separated out and subsequently washed with neutralized water to obtain a crude product. The obtained crude product was dissolved in methanol, treated with activated carbon, and then purified by adsorption column chromatography to obtain the desired diethylene glycol bisphenyl fumarate (DECBPF) and diethylene glycol bisbenzyl fumarate (DEGB z F).
were obtained respectively. Its structural formula and analytical values are shown below.

(DEGBPF) δ=3.58~4.57 ppn+ (8H, -0-C
112CI1.0-)HH Dan=6.76 ppm (411,-C:C-) Tsuji C (DEGB z F) δ=3.62-4.54 ppm (81i,-〇-C
jj2CH20-)=5.21 ppm (4t(,-
CH2-◎)HH HH E=6.77 ppm (411,-C=C)Dan- Diallylphthalate h (DAP), vinyl acetate (VAc), or styrene (St) was added to each of the above diethylene glycol bisfumarates. Add 0.2 g of benzoyl peroxide as a radical initiator using the sealed tube method in 5 g portions,
Bulk polymerization was carried out at 80° C. for 10 hours.

After polymerization, the cured polymer was subjected to Soxhlet extraction using methanol and acetone for 10 hours to determine the polymerization rate and gelation rate.

"Single cold" - 2υri-ku Mine DEGBPF/DAP 92% by weight 91% by market weight
1) E G B P F / S t 88
#85 nDEGBzF/VAc
95 n 93 nDEGBzF/St
92 IT 90 '7 Major Week Examples 3 to 6 Maleic acid monobenzyl ester and maleic acid monoorthochlorobenzyl ester 1+++ol each, 4 g of para-toluenesulfonic acid as a catalyst, 200 g as a solvent.
mQ)-luene was added, and esterification reaction was carried out at 120 to 130°C for 5 hours using 0.5 mol of bisphenol Δdi(diethylene glycol) as the diol.

Thereafter, toluene was distilled off, and using ethyl acetate as a solvent, the product was neutralized and washed with Na, C○, and aqueous solutions. moreover,
After treating the ethyl acetate solution containing the crude product with activated carbon,
Ethyl acetate was removed by distillation and purified by adsorption column chromatography to obtain the desired bisphenol A di(diethylene glycol) bisbenzyl maleate (E P B zM
) and bisphenol A di(diethylene glycol) bis-orthochlorobenzyl maleate (EPCBzM) were obtained. Its structural formula and analytical values are shown below.

(EPBzM) CH3 δ = 1.64 ppm (6H, -C)C ratio 3 = 3.68-4.68 ppm (1611, -〇C,
1-1-2CF;, O-) = 5.22 ppm (
411, CI I2 @) = 6.26 ppm (4
tl, -C=C) H HH ) (H HH HH (EPCBzM) CH3 δ = 1.65 ppm (6H, -C-)C and 3 = 3.68 ~ 4.68 ppm (1611, -〇CH
2CH20-) = 5.36 ppm (4H, -CI(
, -〇) = 6.28 ppm (4H, -C=C-)I Tsuji Tsuji Furthermore, 100 mQ of ethyl acetate and 2 g of morpholine were added to each 100 g of EPBzM and EPCBzM, and an isomerization reaction was carried out at 80°C for 3 hours. Thereafter, the system was neutralized and washed with 1% aqueous hydrochloric acid solution, and ethyl acetate was distilled off. Furthermore, activated carbon treatment,
Purification was performed by adsorption column chromatography to obtain the target bisphenol A di(diethylene glycol) bisbenzyl fumarate (EPBzF) and bisphenol A di(diethylene glycol) bis-orthochlorobenzyl fumarate (EPCBzF), respectively. Its structural formula and analytical values are shown below.

1〈OCH,0 (EPBzF) CH3 δ=], 60ppm (611,C) C ratio 3 = 3.67-4.68 ppm (16H, -QC limit,
CjI, o-) tsubo = 6.91 ppm (411, -C=C-) tsubo I (H HH I-i H HH Q C1l,
0 (EPCF3zF) C 3 δ=], 61 ppm (611, -C)C! (.

=3.68~4.69 ppm (16H, -QCdan2
C tsubo2O-) = 5.22ppm (4H, -CH2-◎
)=7.00 ppm (-C=C-)The above diol bismate and diol bis fumale-1
- DAP in a manner similar to Examples 1-2 for each;
It was copolymerized with St and VAc, and the polymerization rate and gelation rate were determined.

1 Imabe--jp-Bunji EPB zM/St 7]-Weight%
68% by weight E P B z M / D A P
66 n 62 uE P CB z M
/ S t-79It 75 □! EPBz
"/DAP 91 n
88 nE P CB z F / V
A c 87 JJ 83 1/■ΣP
CB z F / S t, 83 rJ
81 ``Practice - Execution 1eta Second, isopropyl fumarate chloride and cyclohexyl fumarate chloride were synthesized in exactly the same manner as in Examples 1 and 2, and further a mixture of 0.5 moJ of these and 0.5111 ol of benzyl fumarate chloride was prepared. 0.5 mol of ethylene duricol was reacted and purified in the same manner as in Examples 1 and 2 to obtain unnamed diol bisfumarates.

The structural formula and analytical values of each target product are shown below.

CG CI+.

(■MiGBiPBzF) Cdan] δ=1.23.1.36 ppm (611,-CH)
C massage.

=4.43 ppm (4 skin-〇〇dan2Cdan2O-)C
H.

=4.67~5.18 ppm (ltl, -CH
)CH.

Tsubo HH HH II C-0C112CI+, ()-C111il (■MiGnctIBzF) =4.43 ppm (4H, -QCdan2Cdan2O-)
= 4.48 ppm (LH, -7C)) = 5.21 ppm (21 (, -CH2O) = 6.92 ppm (4H, -C=C-) (HH) Asymmetric ethylene glycol 0.3 g of diisopropyl peroxydicarbonate was added as a radical initiator using a sealed tube method for each log of bisfumarate, and bulk polymerization was performed at 45° C. for 10 hours.

After polymerization, the resulting polymer was poured into methanol, filtered and washed, and the polymerization rate was determined.

Furthermore, the obtained polymer was subjected to Soxhlet extraction using methanol and chloroform for 10 hours to determine the gelation rate.

Polymerization rate - Gefu conversion - rate EGBiPBzF 73% by weight 67 heavy diffused EGB
cHBzF 67 JJ 62 71 As is clear from the above results, the polymerization rate or copolymerization rate of both diol bisfumarate and diol bismale-h is similar to the gelation rate indicating the crosslinked portion, so crosslinking is possible. It can be seen that the quality is high.

Claims (1)

[Claims] The following general formula (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (1) (In the formula, R_1 and R_2 are the same or different groups, and at least one of R_1 and R_2 is Indicates an ester residue having an aromatic ring, and when only one of R_1 and R_2 indicates an ester residue having an aromatic ring, the other has 2 to 2 carbon atoms.
8 alkyl group or alkenyl group or a cycloalkyl group having 3 to 12 carbon atoms, and R_3 is -(CH_2)n-
, -(CH_2CH_2O)_m-CH_2CH_2-
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ or ▲There are mathematical formulas, chemical formulas, tables, etc.▼. However, n, m, l are respectively 2≦n≦10, 1≦m
Represents an integer of ≦10, 1≦l≦10. ) A diol bis-unsaturated carboxylic acid ester having two polymerizable vinyl bonds in the molecule.