JPS6245561A - Novel diol bisalkyl fumarate - Google Patents

Abstract

NEW MATERIAL:A compound expressed by the formula [R1 and R2 are 2-4C alkyl or 3-12C cycloalkyl (when the carbons linked to the ether oxygen are alphacarbons and the carbons linked to the alpha carbons are beta carbons in the alkyl and cycloalkyl groups, the sum of the beta hydrogen atoms linked to the beta carbons is >=3); R3 is -(CH2)n-, -(CH2CH2O)m-CH2CH2-, etc.; (n and m are as follows; 2<=n<=10, 1<=m<=10]. EXAMPLE:Ethylene glycol bissecondary butyl fumarate. USE:A crosslinking monomer having 2 polymerizable vinyl bonds in the molecule and capable of homopolymerizing by the radical polymerization method to give heat-resistant resins having a crosslinked structure. PREPARATION:A monoalkyl maleate is chlorinated with a chlorinating agent, e.g. thionyl chloride, in the presence of a base, e.g. pyridine as a catalyst to give a monoalkyl fumarate chloride, which is then esterified with a given diol to afford the aimed compound expressed by the formula.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a novel diol bis alkyl fumarate, and more particularly to a novel diol bis alkyl fumarate having two polymerizable vinyl bonds in the molecule.

<Prior art and problems> Conventionally, polyfunctional monomers containing two or more double bonds in the molecule have been used as homopolymers or crosslinking agents to improve the heat resistance, solvent resistance, mechanical strength, etc. of vinyl polymers. Used for quality, etc. Examples of such polyfunctional monomers 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. In addition, di(meth)acrylates are good for styrene, (meth)acrylate, etc., but difficult to use for vinyl chloride and vinyl acetate.
There were 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 provides a crosslinkable polyfunctional monomer that can easily form a crosslinked structure in a polymer structure by radical polymerization, and can also be copolymerized with any monomer such as styrene, vinyl chloride, or vinyl acetate. It is an object of the present invention to provide a novel diol bisalkyl fumarate.

<Means for solving the problems> According to the present invention, the following general formula (1) (wherein R and R2 are the same or different groups,
Indicates an alkyl group having 2 to 8 carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms, and in the alkyl group and cycloalkyl group, the carbon bonded to ether oxygen is α carbon, and the carbon bonded to α carbon is β carbon. , the β bonded to the β carbon
The sum of hydrogen atoms is 3 or more, and R1 is -(cHz)n-1 -(CH,CH20)l,l CH2CH2.

-(c H,CH(c H,)○)m -CH2CH(
CR3) -.

CR3 CH.

Indicates CR3. However, n, m, and Q are each 2≦n≦10゜1≦m
Represents an integer of ≦10, 1≦Ω≦10. ) A diol bisalkyl fumarate having two polymerizable vinyl bonds in the molecule is provided.

The present invention will be explained in more detail below.

The present invention provides a diol bisalkyl fumarate represented by the above general formula (1). R1 and R in the formula
2 is the same or different group, and is an alkyl group having 2 to 8 carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms. When the alkyl group has 9 or more carbon atoms or the cycloalkyl group has 13 or more carbon atoms, polymerizability decreases. In the above alkyl group and cycloalkyl group, when the carbon bonded to the ether oxygen is α carbon and the carbon bonded to the α carbon is β carbon, the sum of β hydrogens bonded to the β carbons must be 3 or more. For example, as shown in the formula below, R or R
When 2 is an ethyl group, there are three β-hydrogens, when it is an isopropyl group, there are six β-hydrogens, but when it is an n-propyl group, there are two β-hydrogens, which are used in the present invention. Can not.

(β hydrogen) H-C-H (β hydrogen) H of isopropyl group (β
carbon) Sum of β hydrogens = 6H-C-CH-0
- (β carbon) (α carbon) (β hydrogen) H-C-C-CH2-0-sum of β hydrogen = 21 (β carbon)
(α carbon) I (β hydrogen) Similarly, when R□ or R2 is a cycloalkyl group, the sum of β hydrogens is as follows.

(β-Hydrogen) (β-Hydrogen) If the sum of β-hydrogens is 2 or less, the polymerizability decreases and it cannot be used. In addition, n, m, Q in R1 of the above formula (1)
each represents an integer of 2≦n≦10.1≦m≦10.1≦Q≦10. When n, m, and Q are 11 or more, it becomes difficult to synthesize one.

Examples of diol bis-alkyl fumarates that can be preferably used in the present invention include ethylene glycol bisisoprobyl fumarate, ethylene glycol bis-starshabutyl fumarate, diethylene glycol biscyclohexyl fumarate, diethylene glycol bisisopropylethyl fumarate, and dipropylene glycol Bisisopropyl fumarate, tripropylene glycol biscyclopentyl fumarate, bisphenol A bis-sec-butyl fumarate, bisphenol A diethylene glycol biscyclohexyl fumarate, bisphenol A di(diethylene glycol) biscyclohexyl isopropyl fumarate, bisphenol A di(diethylene glycol) bisisopropyl Fumarate, bisphenol A dipropylene glycol bisneopentyl fumarate, and the like.

To synthesize the diol bisalkyl fumarate of the present invention, first, monoalkyl maleate is treated with a chlorinating agent such as thionyl chloride, phosphorous trichloride, or phosphorus pentachloride, and a base such as pyridine or triethylamine is used as a catalyst. Synthesize alkyl chloride. Thereafter, it is synthesized by esterifying the fumaric acid monoalkyl chloride and a predetermined diol in the presence of a base such as pyridine or triethyleneamine. It can also be obtained by heat treatment or dehydration and esterification of monoalkyl maleate and a predetermined diol in the presence of an acid catalyst.

By using the diol bisalkyl fumarate 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, for example. It can be carried out by known techniques such as bulk polymerization, suspension polymerization, emulsion polymerization, and solution polymerization. Polymerization or copolymerization is carried out using diisopropyl peroxydicarbonate, diethylhexyl peroxydicarbonate, -butyl peroxypivalate, isobutyryl peroxide, lauroyl peroxide, benzoyl peroxide, as a radical initiator.
This can be carried out using azobisisobutyronitrile, azobisdimethylvaleronitrile, persulfates, persulfate-bisulfite systems, and the like. The radical initiator has an amount of 0.01 to Lol to the diol bis fumarate or the mixture of diol bis fumarate and copolymerizable monomer of the present invention.
lt%.

More preferably, 0.1 to 5 νt% is used, and the polymerization temperature is 3
It is preferable to leave it for about 1 to 72 hours at a temperature in the range of 0 to 100°C.

The copolymerizable vinyl monomers that can be copolymerized with diol bisfumarate in the present invention include styrene, methyl nucleus-substituted styrene, halogen nucleus-substituted styrene, α-methylstyrene, divinylbenzene, vinyl acetate, vinyl chloride,
vinylidene chloride, butyl vinyl ether, ethyl vinyl ether 5 acrylamide, N,N-dimethylacrylamide, ethyl acrylate, methyl methacrylate,
Examples include acrylonitrile, isobutylene, 1,3-butadiene, diallyl phthalate, diallyl isophthalate, and the like.

<Effects of the Invention> The diol bisalkyl fumarate of the present invention is a crosslinkable monomer having two polymerizable vinyl bonds in the molecule, and when homopolymerized by a radical polymerization method, a heat-resistant resin having a crosslinked structure can be synthesized. When copolymerized with other vinyl monomers, it can be used as a crosslinking agent to modify the heat resistance, solvent resistance, mechanical strength, etc. of vinyl polymers.

<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.

<Examples 1 and 2> Triethylamine (1 mol) as a catalyst and benzene (500 mQ) as a solvent were added to each mol of maleic acid monoisopropyl ester and maleic acid monosecondary butyl ester, and thionyl chloride (1 mol) was added in a water bath.
, 2 mol) was added dropwise, then reacted at room temperature for 4 days, the hydrochloride was removed, and the benzene was distilled off.
Fumaric acid monoisopropyl chloride and fumaric acid monosecondary butyl chloride were synthesized, respectively. Furthermore, each of the obtained fumaric acid monoalkyl chlorides was mixed with ethylene glycol (0.4 mol) and pyridine-benzene (1:1).
It was added dropwise to a mixed solution of 300 mQ under a water bath, and reacted at room temperature for 10 hours. Next, the pyridine hydrochloride was separated, the 0 solution was washed with water, then washed with a 1% aqueous hydrochloric acid solution, and finally washed with a 1% aqueous Na 2 CO 3 solution and concentrated to obtain a crude product. The obtained crude product was finally dissolved in methanol and treated with activated carbon, and then purified by adsorption column chromatography to obtain the desired ethylene glycol bis isoprobyl fumarate (EGBiPF) (colorless liquid) and ethylene glycol bis secondary butyl. Fumarate (EGB
sBF) (colorless liquid) was obtained. Its structural formula and analytical values are shown below.

(EGB i P F) H' -NMR CH3 δ=1.23.1.36 (ppm) (12H, -CH
)CH.

=4.43 (4H, -〇-Cdan2C
Dan2-〇-)CHl =4.67-5.18 (2H,-CH)CH3C1-I'-NMR Blue δ=0.85-1.07 (ppm) (6H,CH,
CH2CH-) C mountain = 1.26, 1.37 (6H, -CI-(-) summer = 1.47 ~ 1.91 (4H, CH3Cru CI-
(-)=4.42 (4H, -0-Cdan2C
Lu○−)=4.66~5.20 (2H,−cH2
-Cdan-)H ■ For each of the above ethylene glycol bisalkyl fumarates, 6
Bulk polymerization was carried out at 0°C for 5 hours.

After the polymerization, the resulting polymer was poured into a water-MeOH (1:5) mixed solution and washed, and the polymerization rate was determined.

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

Polymerization rate Gelation rate EGBiPF 47% by weight 43% by weight EGBsB
F 29 ” 27 # As is clear from the above results, the polymerization rate of the monomer and the gelation rate indicating the crosslinked portion are similar, which indicates that the crosslinkability is high.

<Examples 3 to 6> Each fumaric acid monoalkyl chloride was synthesized in exactly the same manner as in Examples 1 and 2, and the following diols were reacted in the presence of a base catalyst in the same manner as in Examples 1 and 2. Purification was performed to obtain the desired purified product.

(Toss T-4: Bao) The analytical values are as follows.

H' -NMR GBiPF CH3 δ=1.22.1.33 (ppm) (12H, -CH
)CH3 ~1.44~1.86 (4H, -0CR2Cdan2C
le CH20-)~3.99~4.21 (4H,-Q
C.G.)CH.

=4.78~5.20 (2H, -C day) CH.

Time = 6.78 (2H, -C=C-) ratio pGB t B F CH3 δ = 1.10~1.41 (ppm) (6H, -〇H
-0-)CH3 ~1.49 (18H, -C-CH,)CH3 CH3 ~3.55-4.02 (4H, -QCdan2CH-)
CH.

=5.05~5.41 (2H, -0CH2Cdan-)
= 6.68 (2H, -C=C-) ■ PBiPF CH3 δ = 1.27, 1.35 (ppm) (12H, -CH)
CH.

C! i3 ~1.65　(6H,-◎-C-◎-)嘗 C)(.

~3.68~4.55 (16H, -OCdan2Cdan2
O-)CH.

=4.77-5.18 (2H, -CH)CH.

■ =6.70 (2H, -C=C-) [danCH3 ■ =l, 06~1.42 (12H, -0CHCH2-
)CtanJ ~1.64 (6H, -〇-C-〇-)CH3 ~3.55~4.03 (8H, -QCdan2CH-)
Dan = 5.04 ~ 5.42 (4H, -OCH, C Danji)
First, 5 g each of diallyl phthalate (DAP), vinyl acetate (VAc), or styrene (St) was added to each diol bisalkyl fumarate using the sealed tube method, and 0.0 g of benzoyl peroxide as a radical initiator was added to each diol bisalkyl fumarate. 15g was added and bulk polymerization was carried out at 80°C for 10 hours.

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

Polymerization rate Gelation rate BGBiPF/DAP 97% by weight 92% by weight PG
BtRF/DAP 95 II 93 nE
P B i P F / V A c 96”
94 IIP P B c HF / S t
94'l 93 # As is clear from the above results, the polymerization rate of the monomer and the gelation rate indicating the crosslinked portion are similar, which indicates that the crosslinkability 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 the number of carbon atoms is Indicates an alkyl group having 2 to 8 carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms, and in the alkyl group and cycloalkyl group, the carbon bonded to the ether oxygen is an α carbon, and the carbon bonded to the α carbon is a β carbon. , the sum of β hydrogens bonded to β carbon is 3 or more, and R_3 is -(CH_2)
_n-, -(CH_2CH_2O)_m-CH_2CH_2-,
-[CH_2CH(CH_3)O)_m-CH_2CH
(CH_3) −, ▲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≦
Represents an integer of m≦10, 1≦l≦10. ) A diol bisalkyl fumarate having two polymerizable vinyl bonds in the molecule.