JPS5949207A - Chlorosulfonated polyolefin type copolymer - Google Patents

Abstract

PURPOSE:The titled novel copolymer, obtained by chlorosulfonating an alkylene- alkyl (meth)acrylate copolymer, etc., having improved flexibility, transparency, etc., without containing a plasticizer, and useful in the field of medical equipment. CONSTITUTION:A novel chlorosulfonated polyolefin type copolymer obtained by chlorosulfonating (A) an alkylene-alkyl (meth)acrylate copolymer, (B) an alkylene-alkyl (meth)acrylate-(meth)acrylic acid copolymer or (C) an alkylene-alkyl (meth)acrylate-maleic acid (anhydride) copolymer to give 0.15-5wt% content of sulfur and 5-50wt% content of chlorine. A compound of the formula (R<1> is H or CH3; R<2> is 1-8C alkyl) is preferred for the alkyl (meth)acrylate monomer be used, and ethylene or octene-1, etc. is preferred for the alkylene.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to chlorosulfonated polyolefins, and more particularly to '111' lorsulfonated polyolefins transparently drenched to lI''f.

Conventional chlorosulfonated polyolefins include polyethylene, polypylene, ethylene-propylene-t”i
It is a random chlorine-substituted or sulfonyl chloride-substituted polyolefin such as ff-coalescence, and has various physical properties ranging from hard plastic-like to soft rubber-like depending on the chlorine content and sulfonyl chloride a, and has weather resistance. It has special characteristics such as 1-class maison property, bending fatigue resistance, flame resistance, blood abrasion resistance, 1- madder quality, oil resistance, and color stability. However, the transparency of the conventionally known chlorosulfonated polyoleinine was not necessarily sufficient, and it was not suitable for applications requiring transparency.

On the other hand, in recent years, 44 materials have been praised for their flexibility, impact resistance, and transparency.
There is a strong demand for the appearance of soft polyvinyl chloride resin, which has flexibility and transparency. However, polyvinyl chloride I:4 resin moldings containing riJ'9VJ agents such as Di'Kuburfuk 1/-1 are difficult; There are 421 medical devices (111) in 10 cases (711 cases where soft polyvinyl chloride resin is used).
This is considered a major drawback. In particular, when soft TC polylj, i-mount vinyl, etc. are brought into contact with blood, etc., the il plasticizer from the resin will transfer to the blood, etc.
It might be. 1-mae is soft polyvinyl chloride li'fJ
In the medical phrenology field, where materials 1 are widely used, there is a strong need for the emergence of materials 44 that are flexible and immersed in transparency, with no worries about the migration or release of materials such as plastics. ing.

The present invention has been made in view of the
'5] Contains no plasticizers, and is flexible, transparent, cloudy, soil weather resistance, ozone resistance, bending fatigue resistance,
The purpose of this invention is to provide a new chlorosulfonated polyolefin that has excellent properties such as abrasion resistance, oil resistance, and high frequency weldability. Alkyl methacrylate or alkyl acrylate [hereinafter abbreviated as alkyl (meth)acrylate] Copolymer (B) Alkylene-(meth)acrylic alkyl-methacrylic acid or acrylic acid [hereinafter abbreviated as (meth)acrylic acid] Copolymer or (C) alkylene-alkyl (meth)acrylate-
Chlorine with a sulfur content of 0.15 to 5% by weight and a chlorine content of 5 to 50% by weight, obtained by sulfonating a copolymer of maleic anhydride or maleic acid [hereinafter abbreviated as [maleic anhydride]]. This is achieved by means of sulionized polyolefins.

The copolymers (A), (B), and U used in the present invention include alkylene, alkyl (meth)acrylate, alkyl (meth)acrylate and (meth)acrylic acid, or alkyl (meth)acrylate and (anhydride). ) A known compound which forms 'C' by reaction with maleic acid or, in some cases, by (partial hydrolysis reaction of the alkyl methacrylate group of the AJ copolymer), with an appropriate amount of about 2 to about 50 ji 41% of bound (meth)acrylic acid, 0-20% of bound (meth)acrylic acid, 0-5% of bound (meth)acrylic acid, 0-5% of bound (meth)acrylic acid, 41
do.

Suitable alkylenes include ethylene, propylene, butene-1, isobutylene, pentene-1,2-methylbutene-7,6-meb-lupden-1, hexene-1, heptene-1, octene-1, and the like. It is also possible to use two or more of these.

The algylene moiety of the copolymers (A), (B), and (C) has at most 18 carbon atoms, preferably 2 to 5 carbon atoms.
It has 1 carbon atoms.

A suitable alkyl (meth)acrylate monomer which is combined with alkylene in 1 has the following formula % formula % (1) [In the above formula, R1 is a hydrogen atom or a methyl group, and R is 1 to 8 is an alkyl group having carbon atoms. ]. Examples of specific compounds covered by this formula (1) include methyl (meth)acrylate, (meth)
Acrylic ethyl, (meth)acrylic n-butyl, (
t-butyl meth)acrylate, 2-(meth)acrylate
Examples include ethylhexyl.

The above (A), (B) and (0) copolymers generally include:
a density of about 0.92 to 0.94, and a density of about 0.5 to about 500
It has a melting index of dV.

The production method for obtaining the chlorosulfonated polyolefin of the present invention by chlorosulfonating the (A), (B) or (C) copolymer is not particularly limited, and generally (A), (B) or (C) A bath liquid method in which the copolymer is dissolved in an organic solvent and chlorinated and chlorsulfonated using chlorine and sulfur dioxide gas or chlorine sulfuryl chloride, and powdered at a temperature of 0 to 80°C. The fA), (B) or (C) copolymer is reacted with gaseous chlorine and substituent (Ii:e acid gas) to form chlorosulfonate by a gas phase method, and then this reaction product is produced. Gas phase water F-!b rM 1% characterized by adding 9V of chlorine at 60 to 150℃ in aqueous @lN form.
The lI combination method combination-shift jjM manufacturing method may be adopted.

(A), fL3) or CG) chlorsulfonated copolymer to obtain chlorsulfonated polykaryrefine (A), (B) or (0)
The degree of chlorsulfonation of the copolymer is chlorinated 1 u]5~
5 [I Jj'1ijijiA, rio /shiy, /l
/ 7-t :'f); IAj &'11++if
i li containing' M Ic 0.15-5, 0
, +ji, i, f%, and f is exactly 7 to 451
j hlj' % degree of chlorination, degree of chlorsulfonation 'J, I! ';f)'￥ Contains'('J Jli is 0.15 to 4 Jli,,', jfi-% is l1 and 1); (:Contains 1.; is! i jll
, less than iJ% a) when &;1-j5! Meisaku, letter of construction 1
This 1: Or rubbery 'l゛! Y jll mi drops, book i
b rjIJ tjr! It is not possible to achieve the IJ objective of IJ, and when it exceeds 50 weight 1.
The present invention 7Ji
unable to achieve the desired goal. In addition, when the sulfur content HL exceeds 5% by weight, lack of stability causes discoloration, and when vulcanization is performed using chlorsulfone groups as the vulcanization point, it causes overvulcanization, and when it is less than 0.15% by weight, When it is,
Chemical reactions utilizing chlorsulfone groups, such as various vulcanization reactions, reactions between hydroxyl group-containing compounds and chlorsulfone groups, etc., are insufficient, and the effects of containing chlorsulfone groups are insufficient.

The chlorosulfonated polyolefin copolymer of the present invention has ambiguous transparency compared to ordinary polyolefins such as chlorosulfonated polyethylene, polypropylene, and ethylene-propylene copolymers, so transparency is required. Suitable for applications such as In addition, unlike soft polyvinyl chloride resin, it does not contain a plasticizer, so even if it is used in the medical device field, there is no need to worry about the transfer of R+J plasticizer (it is used as a flexible and transparent resin, and furthermore, according to the present invention Because the copolymer contains an ester group, or in some cases an ester group and a carboxylic acid group, its adhesion to various base materials is unclear, and its solubility in various organic solvents and high IS This is a novel chlorosulfonated polyolefin copolymer.

The fields of application of the 04 combination provided by the present invention are its excellent mechanical properties, flexibility, transparency, weather resistance, +tiJ ozone resistance, I11+ resistance, bending fatigue resistance, abrasion resistance, and high frequency welding properties. and 14. It can be used alone or as a blend with fine combinations, general-purpose rubbers, inorganic fillers, etc. by taking advantage of its adhesion properties, and it can also be used for various industrial products by taking advantage of its solubility and r properties in various organic solvents. It can be widely used in rubberized fabrics, shoe soles, rubber tiles, building materials, wheel supplies, electrical appliance parts, medical supplies, etc.

The copolymer of the present invention is also capable of 41-fold crosslinking using chlorsulfone groups, ester groups, and carboxylic acid groups, and perogylide crosslinking using peroxide. Furthermore, the synthetic resin of the present invention may contain antioxidants, ozone deterioration inhibitors, ultraviolet absorbers, tackifiers, mold release agents, softeners,
It is of course possible to use agents such as reinforcing agents, fillers, and other agents such as coloring agents.

Next, the present invention will be explained in more detail according to examples. In addition, various physical property values in Examples were measured by the following methods.

(1) Salt content and sulfur content (degree of chlorination, degree of chlorsulfonation): After producing a sample piece by press molding, it was measured using a fluorescent X-ray analyzer manufactured by Rigaku Gunki Kogyo Co., Ltd.

(2) Mechanical strength (tensile test); JIS K 6 using test pieces prepared by press molding
A tensile test was conducted according to the specifications of 3Q1. The tensile testing machine is Tensilon UTM-1 manufactured by Toyo Sokki Co., Ltd.
1 [Using a mold, it was pulled at a speed of 5 otnm/min.

(3) Transparency: Haze was determined using a haze meter manufactured by Suga Test Instruments Co., Ltd. using a sample prepared by press molding to a thickness of ITrrIn.

(4) O
6 using Abbe Refractometer
It was fixed at +1J.

(5) High frequency welding property: Using a film prepared to a thickness of 0.5 to 0.5 mm, the 'C film was bath-deposited on Frequency Welder KV 3000 TA manufactured by Shigeko Kogyo Co., Ltd., Kozue City. The strength was measured as 180°-clinch strength.

(6) MI of copolymer Temperature 190C1 Machining 2.1 (Sky, 7cn?
Measured in '.

Mitsuichi 1 0-1 refrigeration pipe, ノ) 1'16 machine, temperature gauge, gas η
2. In a separable flask equipped with an entry tube, add 90% carbon tetrachloride (19.
'￥Z Methyl J1 Mi I1i 1 bottle (1 eyebrow phase; Engineering (I)) A Prisoner , ratio 11 (0,
955) 100 & was heated to 75 to 76 to dissolve the copolymer.

Then (F anti-J1゛, - the pregnant air in the vessel was sufficiently replaced with nitrogen gas) 11, 1 to the waste from the person'θ, (Bonju gas, !ll
j Mixture of silicic acid gas 'rt Jj '<, 511. )t
If(J,) f, one-C2,j%, the copolymer was chlorosulfonated. The introduction ratio of the mixed gas is 413/Hr for chlorine gas and 81/Hr for sulfur dioxide gas.
Met. After that, the introduction of gas was started, and unreacted chlorine, sulfur dioxide gas, and by-product hydrogen chloride in the solution were removed.
While blowing nitrogen gas, the mixture was removed at 75 to 77°C for 2 hours, methanol was added to precipitate the chlorosulfonated product, and after washing with methanol and drying, a chlorosulfonated copolymer was obtained.

Contains chlorine, i: ; 12.8
%Sulfur content %f; 0.26%
Film tensile test; Ml 00 3
o, 5k11/cnr'M300 3
a, ykg7cn? Cutting depth (%) 910% Cutting strength 107.9ky/crrr”Haz
e; 1
8.3% refractive index: 1.49
8 High frequency welding property: Good welding was achieved, and in the 180° peeling test of the welded part, the base film was cut.

Dono [no1lif>! I-2 Ethyl-methacrylic tT Kumetel-anhydrous malein 1)
135-3, including methacrylic resistant mebble) 7) 2.3%,
fBN' containing maleic anhydride, 0.35%, MI=3
．． 2) 100y1 carbon tetrachloride 900,? 2! - The mixture was charged into a separable 7-glass bottle, dissolved, and chlorosulfonated in the same manner as in Example 1 to synthesize chlorsulfonated copolymer a. However, the mixed gas introduction liquid is 12e/
Ratio of Hr (chlorine gas 4-9/Hr.

slK ME Cj: 2 gas 8, I3/Hr)
At 6 o'clock, 1t4J If there were people.

Chlorine statement: 18.2% Sulfur content: 0. ! 12% film tension test; Mloo 37.0k
y/cn12M300 48.5ky/1yn
2 cuts 1 cut 1 medium (%) 800% Cutting strength 130.5kl/cat'Haze
;2
7% refractive index; 1.4
9 High frequency weldability; good bath adhesion, welding 180 of 1113
゜In the peel test, the base material broke.

Example-3 Copolymer powder (XM-135-4 ethylene-methyl methacrylate copolymer Pulverize the combined material using a turbo mill, with an average particle size of 4.
5 mesh of copolymer powder) 7 starch was charged, sealed, replaced with nitrogen, and stirred at 120 revolutions per minute to ensure sufficient fluidization. The jacket of the autoclave was kept at 30 to 35° by sufficiently flowing cooling water.

Sulfur dioxide gas was added to this autoclave at 30°C, and the pressure was 3.
．． 0 k,y 7 at? ' was press-fitted. Continued 3
At 0"C, add chlorine gas to a further pressure of 4.0 kg/c
It was press-fitted until it became 17+2. After 3 hours of reaction, the pressure is 2
．． The blood pressure was lowered to 97cm2 on June 6th. Exhaust unreacted gas,
The gas adsorbed on the chlorosulfonated copolymer was separated. After that, 80 μm of pure water in which 180 I of sodium dodecylbenzenesulfonate was dissolved was further charged into the autoclave, and the chlorosulfonated copolymer was dispersed in the water, and the water was thoroughly replaced with nitrogen. White, increase the internal temperature to 90"C and add chlorine gas 5.
A pressure of 0 kl/Cm2 was introduced, and this pressure was maintained for 3 hours to conduct the reaction. Make-up brine gas was approximately 2.5 #. Then, the reaction temperature was further increased to 1 os'C, and the chlorine gas pressure was increased to 5,0 ky, / crr? Hold and react 1
child. Make-up brine gas was approximately 2.9 kp. Next, the reaction system was cooled and unreacted gas was exhausted, and the obtained chlorosulfonate was collected, thoroughly washed with hot water at 70°C, and then dried under reduced pressure at 50°C. The product was a pale yellow amorphous nidistomer.

Chlorine content; 22.0% stuttering content; 0-53% ratio Nail y i, i
o6 Firno 1 tension test; λ (1007k1/cr7
? M30υ 71 Cut 1vr Offset % 1500% Cutting strength Haze without cutting; 18.
2% refractive index* 1.49
B: High frequency weldability: Good welding was achieved, and in a 180° peel test of the welded part, the base material was broken.

Comparison de jl-1 High-density polyethylene is converted to chlorsulfmen by a gas phase method,
Manufactured by chlorination using the water suspension method.

Lorsulun ionized polyethylene (Elasulun XC34Q
IAS chlorine content 39.5%, sulfur content 0.84%, d=
1.2o) showed the following physical property values.

Chlorine content j, i; 59.5% sulfur content: &t O, 84% film tensile test; Ml 00 8. y
k17crr? 'Cutting elongation 800% Cutting strength 100 kg/Crn2Haze
76.0% polysulfonated polyethylene
Although no residual crystallinity was observed in (DSC) measurements, the transparency was poor and haze
The value was 76.0%. In addition, when we tested the high frequency weldability of the films under the same conditions as in Example 1, the films appeared to be well welded to each other, but in the 180° peeling test, they peeled off easily and their strength was poor. was 0-5 to 1 ky, /25 ky.

lrS permit applicant Wadenko Co., Ltd. Substitute Yoshihiro Sato, Ben-Konshi

Claims (1)

[Scope of Claims] (A) Alkylene-methacrylic self-adjusted alkyl alkyl acrylate copolymer (BJ fullkylene-alkyl methacrylate), alkyl acrylate-methacrylic acid or acrylic acid copolymer, or (0) Al-V-rene-alkyl methacrylate or alkyl acrylate-maleic anhydride or maleic acid co-j1 (I-
゛　Lt (1. 1 5~5 2ft '74i
%, chlorine content 5-50% - 11.1% chlorsulfonated polyolefin co-claw union □