JPH01305052A - Polyfluoroalkylpolyoxyalkylene (meth)acrylate - Google Patents

Abstract

NEW MATERIAL:A polyfluoroalkylpolyoxyalkylene acrylate and methacrylate expressed by formula I (Rf is 1-20C polyfluoroalkyl; R is 1-5C alkylene; AO is one or two or more 2-18C oxyalkylene groups and may be added in a block or random form in the case of two or more kinds thereof; R is H or CH3; n is 1-50). EXAMPLE:An ester expressed by formula II. USE:A monomer for copolymerization, excellent in compatibility and capable of readily introducing polyfluoroalkyl groups into polymers. PREPARATION:For example, an alkylene oxide is subjected to addition reaction with a polyfluoroalkyl alcohol expressed by the formula RfROH and esterification reaction with acrylic or methacrylic acid or ester interchange reaction with the methyl ester thereof, etc., is carried out to afford the compound expressed by formula I.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a fluorinated fulkyl-based acrylic monomer containing a polyfluoroalkyl group and a polyoxyalkylene group in the molecule.

[Conventional technology]

Conventionally, fluorinated alkyl-based 7-acrylic monomers containing a polyfluoroalkyl group include ◆2-perfluorophexylethyl ◆methacrylate and acrylate (hereinafter, both acrylate and methacrylate are referred to as (meth)7-acrylate5), -Perfluorooctylethyl (meth)acrylate, 2.2.3.3-tetrafluoropropyl (meth)acrylate, 2,2,3,4
, 4°4-hexafluorobutyl (meth)acrylate and the like are known, and resins obtained by homopolymerization and copolymerization of these are used in a wide range of fields.

[Problem to be solved by the invention]

However, these fluorinated alkyl-based heptacryl monomers have extremely poor compatibility with other organic compounds due to their polyfluoroalkyl groups, which not only limits the solvents that can be used, but also limits compatibility with other monomers. As a result, the type and amount of copolymerization monomers to be used are limited, and the properties of the polyfluoroalkyl group cannot be fully utilized.

Furthermore, for example, when 2-perfluorooctylethyl acrylate is solution-polymerized alone to form a film, it is characterized by very low tackiness, but this may be a drawback depending on the purpose of use.

Furthermore, conventional fluorinated acrylic monomers contain only so-called hard segments, and the only way to introduce a soft segment into a polymer is to use a copolymerization reaction.

The purpose of the present invention is to improve the heat resistance, weather resistance, chemical resistance, water and oil repellency, low refractive index, low dielectric constant, low friction coefficient, high gas permeability, low surface tension, etc. unique to polyfluoroalkyl groups. By adjusting the type of alkylene oxide to be added and the number of moles added while taking advantage of its properties, soft segments and semi-soft segments can be freely included in the molecule.
supplying crylic monomer. This K adjusts the compatibility of the polymer with solvents and other monomers, adjusts the mechanical strength, and imparts properties such as moderately improving the adhesion of the polymer with other materials. At the same time, the percentage of fluoroalkyl groups can be balanced.

[Means to solve the problem]

The present invention is a polyfluoroalkylpolyoxyalkylene (meth)acrylate represented by general formula (1).

R4RO(AO)nCOC(R1)=CH2...
...... (1) (However, Rf is a polyfluoroalkyl group having 1 to 20 carbon atoms, and R is a polyfluoroalkyl group having 1 to 5 carbon atoms.
straight or branched fullkylene group, AO is one or more oxyalkylene groups having 2 to 18 carbon atoms;
When it is a species or more, it may be added in a boot stock pattern or in a random pattern, R is H or CH3, and n is 1 to 50. ) In the general formula (1), the polyfluoroalkyl group having carbons a1 to 20 represented by %Rf, for example,
CFs (CFz)p, (CF's hcF(C
Fz )q , HCF2 (CF2 )r, F2(
CF2), etc. (However, p is 0 to 1
q is an integer from 0 to 17, r is an integer from 0 to 19, and S is an integer from 0 to 19. ) Jl-wise, triple oromethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, undecafluoropentyl, tridecafluorohexyl, pentadecafluoroheptyl, heptadecafluorooctyl, nonadecafluorononyl, heneicosa Fluorodecyl, tricosafluoroundecyl, pentacosafluoroundecyl, heptathafluorotridecyl, 7 naphthafluorotetradecyl, hentriacontafluoropentadecyl, tritri7contafluorohexadecyl, pentatriacontafluoroheptatecyl, heptatria Contafluorooctadecyl, nonatri-7juntafluorononadecyl,
Hentetracontafluoroeicosyl, monohydrodifluoromethyl, ω-hydrotetrafluoro p-ethyl, ω-
Hydohexafluoroppvir, H-hydroctafluorobutyl, ω-Hydrodecafluoropentyl, ω-Hydrododecafluorohexyl, ω-Hydrodecafluoropheptyl, ω-Hydrohexadelph-Ileoooctyl , ω-human-octadecafluorononyl, ω-hydroeicosafluorodecyl, ω-hydrodocosafluoroundecyl, ω-hydrotetracosafluorododecyl,
ω-human a-hexacosafluorotridecyl, ω-hydrooctacosafluorotetradecyl, ω-hydroditriafuntafluoropentadecyl, ω-human p-dotriacontafluorotuhexadecyl, ω-human p-tetratriacontafluorohepta Decyl, ω-hydrohexatriacontafluorooctadecyl, ω-human poctatriacontafluorocinonadecyl, ω-human cutitracontafluoroeicosyl, 7klff-difluoromethyl, ω-chlorotetrafluoroethyl, ω-chlorohexa Fluoropropyl, ω-atS octafluorobutyl, ω-chlorodecafluoropentyl, ω-chlorofluorohexyl, ω-chlorotetradefluoroheptyl, ω
-ri aa hexadecafluorooctyl, ω-ri tip octadecafluoro O/nyl, ω-ri a+=+eicosafluoro w decyl, ω-chloro I-tofsafluoro p undecyl,
ω-ri p lotido fluorododecyl, ω- clohexacosafluor p tridecyl, ω- clo octafuthafluorotetradecyl, ω-ri p lotriacontafluor p
Pentadecyl, ω-ri RP dotri7 juntafluorohexadecyl, ω-ri aa tetratria puntafluoroheptadecyl, ω-chlorohexatriafuntafluoro p octadecyl, ω-ri pp octatriacontafluoro p nonadecyl, ω-chlorotetraconta fluoroeicosyl,
inheptafluoropurvyl, 2-trifluoromethylhexafluoropropyl, 3-trifluoromethyloctafluorobutyl, 4-trifluoromethyldecafluoropentyl, 5-)lifluoromethyltotecafluorophexyl, 6-)! 7-fluoromethyltetradecafluorohbutyl, 7-)lifluoromethylhexadecafluorooctyl, 8-trifluoromethyloctadecylnonyl, 9-trifluoromethyldocosafluorodecyl, 10
-trifluoro p-methyldofusafluoroundecyl, 11
-trifluoromethyldetracosafluorododecyl, 1
2-) Lifluoromethylhexacosafluorotridecyl, 13-) Lifluoromethyloctafuxafluorotetradecyl, 14-) Lifluoromethyltriacontafluoropentadecyl.

15-Trifluoro p-methyldotriafuntafluorohexadecyl, 16-)lifluoromethyltetratriacontafluoro-pheptadecyl, 17-dolifluoromethylhexatriacontafluoro-poctadecyl, 18-trifluoromethyloctatriacontafluorononadecyl and so on.

Examples of the alkylene group having 1 to 5 carbon atoms represented by R include linear or branched fullkylene groups such as methylene group, ethylene group, propylene group, butylene group, and pentylene group.

The oxyalkylene group having 2 to 18 carbon atoms represented by AO includes oxyethylene group, oxypropylene group, oxybutylene group, oxybutramethylene group, oxystyrene group, and oxyalkylene group.

Examples include oxytetradecylene group, oxyhexadecylene group, and oxyoctadecylene group.

The compound of general formula (1) can be prepared by, for example, addition reaction with polyfluoroalkyl alcohol (R4ROH) K alkylene oxide, and then esterification reaction with acrylic acid or methacrylic acid or transesterification reaction with its methyl ester. It can be manufactured using a method.

〔Effect of the invention〕

Since the fluorinated alkyl-based acrylic monomer of the present invention has an oxyalkylene group introduced, its compatibility with monomers for copolymerization is improved, and it is easier to use it in a copolymerization reaction to convert a polyfluoroalkyl group into a polymer. can be introduced.

In addition, the surface of the obtained polymer retains the properties of the polyfluoroalkyl group, and depending on the type of oxyalkylene group and the number of moles added, it can be imparted with properties such as adhesiveness and moisture retention, and is water and oil repellent. Antifouling processing, optical materials, paints, 7-otoresists, magnetic tapes, magnetic disks, surface modification of synthetic resins, waterless lithographic printing, medical polymer materials, selectively permeable membrane materials.

A wide range of applications are possible for conductive materials, antistatic materials, and batteries.

〔Example〕

Next, the present invention will be explained by examples. Note that q and ratio indicate the amount of t.

Example 1 Trifluoroethanol (molecular weight 100
) 330JK and a 48J sodium hydroxide aqueous solution 3.3F as a catalyst, ethylene oxide 4807 was introduced under nitrogen atmosphere at 80 to 90C over 2 hours, and the reaction was continued for another 4 and a half hours. U got off.

Next, the reaction product is distilled (72-170[,2++w
a) Ig) to obtain a distilled amount of 730y. (Hydroxyl value 24
0, average molecular t240).

The distillation amount was 432y and methacrylic acid was 232jig.

As a catalyst, para-toluenesulfonic acid-aqueous phase 20,1
Hydroquinone mo/methyl ethyl 0.6 as a binding agent
1 and 500 g of toluene as a solvent were placed in a flask, and an esterification reaction was carried out at reflux temperature in an air atmosphere for 10 hours. After the reaction is complete, a slightly excess 10% sodium carbonate aqueous solution 500F of the neutralization equivalent of the catalyst and methacrylic acid is gradually added to neutralize the reaction, and then washed several times with 80C of a saturated sodium chloride aqueous solution of 500F to give a concentration of 80 to 110%
After removing the solvent and dehydrating with 0C130ffillH, filtration was performed to obtain 440 grams of crude ester.

This crude ester was distilled under reduced pressure (63-6tC, 3■Hg)
Purified ester 102F was obtained.

The analytical values of the obtained ester are shown in Table IK, and the IR spectrum is shown in Figure 1. This ester has the following formula (%). Take diethyl ether complex 7.4F and add 30f+ propylene oxide 128F at 60C under nitrogen gas atmosphere.
The reaction was continued for an additional 1.5 hours. Next, the reaction product was distilled under reduced pressure (93-98 C, 1 mmHg
) Distilled product 150F was obtained from L (hydroxyl value 106, average molecular weight 531).

This distilled product 120F, methacrylic acid 146F, and para-toluenesulfonic acid hydrate 8y as a catalyst.

Fetch 7 Gin 0125F as a polymerization inhibitor and toluene 200F as a solvent were added to a flask.

The esterification reaction was carried out at reflux temperature for 10 hours in an air atmosphere. Next, in the same manner as in Example 1, 91 ml of neutralized ester was obtained to obtain crude ester 180F, and further, vacuum distillation (98 to 110
C%1■Hg)1. 83 refined esters were obtained. The analytical values of the obtained ester are shown in Table 1, and the IR spectrum is shown in Figure 2.
This ester is represented by the following formula.

C, Fl, C2H40C3H60COC(CH3)=C
H2 Example 1 In the same manner as in Example 2, a mixture of perfluorooctylethyl alcohol 464PK, propylene oxide 638P and tetrahydrofuran 395y was subjected to an addition reaction using 10 parts of boron diethyl ether complex. Next, the mixture was neutralized with an aqueous solution of 104 sodium bicarbonate, washed with a saturated aqueous solution of sodium chloride, dehydrated, and filtered to obtain an etherified product (hydroxyl value 35.4, average molecular weight 1586) 1450F.

Next, in the same manner as in Example 2, the etherified product 1450
y, 98.95 g of acrylic acid, para-toluenesulfonic acid-aqueous phase 46P1 hydroquinone monomethyl ether 1.
After carrying out an esterification reaction using 5P and toluene 1200F, the product was neutralized and purified in the same manner as in Example 1 to obtain ester 1180F.

The analytical values of this ester are shown in Table IK, and this ester is represented by the following formula.

C6Fl7 C2H40((C3H60) 6 (CH
2CH2CH2CH2O) 1(1) COCl+=c
H2 Example ζ In the same manner as in Example 3, α-■, α-H0ω-H perfluoroundecyl alcohol (molecular weight 532) 53.
After carrying out an addition reaction of propylene oxide 226F to 2jE using boron trifluoride diethyl ether complex 27, neutralization, washing with water, dehydration and filtration were carried out in the same manner as in Example 3 to obtain an etherified product (hydroxyl value 24.5, 205F (average molecular weight: 2290) was obtained.

Next, in the same manner as in Example 2, the etherified product 200F
, 7acrylic acid 9.4f, paratoluenesulfonic acid hydrate 6.3p, hydroquinone monomethyl ether 0,
After carrying out an esterification reaction using 21 and toluene 160F, the product was neutralized and purified in the same manner as in Example 1 to obtain ester 178F.

The analytical values of this ester are shown in Table IK, and this ester is represented by the following formula.

HCl6F20CH20(C3HaO)3ocOcH-
CH2 table 1

[Brief explanation of the drawing]

FIG. 1 is an IR spectrum diagram of the ester obtained in Example 2. Patent applicant: Nippon Oil & Fats Co., Ltd. “n-layer 17”

Claims (1)

[Claims] 1. Polyfluoroalkylpolyoxyalkylene acrylate and methacrylate represented by general formula (1). R_fRO(AO)_nCOC(R^1)=CH_2・
・・・・・・・・・・・・(1) (However, R_f is a polyfluoroalkyl group having 1 to 20 carbon atoms, R is a linear or branched alkylene group having 1 to 5 carbon atoms, and AO is a carbon One or more types of oxyalkylene groups of numbers 2 to 18, and when two or more types, they may be added in a block form or randomly added,
R is H or CH_3, and n is 1 to 50. )