JPH0241307A - Production of organopolysiloxane-modified copolymer - Google Patents

Abstract

PURPOSE:To obtain a novel copolymer, excellent in water repellency, antifouling properties and weather resistance and useful as a textile water repellent, waterproofing agent, icing inhibitory coating, etc., by polymerizing an ethylenically unsaturated monomer in the presence of a thiol group-containing organopolysiloxane compound. CONSTITUTION:The objective copolymer obtained by copolymerizing 100 pts.wt. ethylenically unsaturated monomer [e.g., methyl (meth)acrylate] in the presence of 0.01-50 pts.wt., preferably 0.1-30 pts.wt. thiol group-containing organopolysiloxane compound (e.g., a compound expressed by the formula).

Description

Detailed Description of the Invention [Industrial Application Field 1] The present invention relates to a method for producing an organopolysiloxane-modified copolymer by polymerizing an ethylenically unsaturated mff1 substance in the presence of an organopolysiloxane containing a thiol group. More specifically, in the presence of an organopolysiloxane having a thiol group at the molecular end or side chain, a chain transfer reaction of a polymer radical to a thiol group is used to polymerize lJ4 or two or more ethylenically unsaturated monomers. A block copolymer of organopolysiloxane and an ethylenically unsaturated monomer or a graft copolymer having organopolysiloxane as the main chain and ethylenically unsaturated Ii tetramer as the side chain, FB type graft j%1 The present invention relates to a method for producing a copolymer (hereinafter collectively referred to as an organopolysiloxane-modified copolymer).

The organopolysiloxane moiety in the organopolysiloxane-modified copolymer described above is a novel organopolysiloxane-modified copolymer that has surface migration properties and imparts water repellency, weather resistance, and stain resistance. be.

[Conventional technology and gap to be resolved 1] In recent years, in the field of polymer synthesis, divine polymers with excellent functionality have been synthesized. Among them, certain block polymers, graft polymers, and comb-shaped polymers are already known as those having surface migration properties. However, when synthesizing these polymers, the yield of the target product is poor, the reaction is complex and involves multiple steps,
Furthermore, it has the disadvantage of being high in cost.

Therefore, as a result of conducting research to easily and inexpensively produce a new polymer with surface migration properties, the present inventor discovered the existence of an organopolysiloxane having a thiol group at the molecular end or side chain as a chain transfer agent. IM or 2f of ethylenically unsaturated monomer below! The present invention has been completed based on the discovery that an organopolysiloxane-modified copolymer having desired properties can be obtained by combining one or more of them.

[Means for Solving the Problems J: That is, 1. The present invention provides an edylenic unsaturated monomial body 100ff
For Tff1 part, add 1 thiol group to the terminal or side chain.
A radical polymerization initiator is used in the presence of 0.011 parts to 50 parts, preferably 1 part to 30 parts of organopolysiloxane containing 1 or more parts, and a chain transfer reaction is carried out using a radical polymerization initiator. It has been discovered that a novel polymer having 1-surface migration property can be obtained by producing an organopolysiloxane-modified copolymer.

[Function] The novel organopolysiloxane-modified copolymer of the present invention is an organopolysiloxane-modified copolymer containing one or more thiol groups at the terminal or side chain instead of the low molecular weight thiol that is usually used as a molecular mJi moderator for radical polymerization. This method uses polysiloxane to produce an organopolysiloxane modified copolymer consisting of a polymer or copolymer of ethylenically unsaturated monomers and organopolysiloxane through a chain transfer reaction. be.

The organopolysiloxane-modified copolymer obtained here is thought to have the following side effects.

That is, when the organopolysiloxane has a thiol group at the molecular end, it becomes a block-type copolymer.

When a thiol group is present in the side chain of the organopolysiloxane, if there is one thiol group, CI.

C11゜ C1l, (C1flllllCI! ) to form a graft-type copolymer.

Furthermore, when there are many thiol groups in one molecule, The comb becomes a copolymer.

Each component used in the present invention will be specifically explained below.

Typical examples of ethylenically unsaturated monobottles used in the present invention include methyl acrylate, ethyl acrylate,
Propyl acrylate, isopropyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, 01-CI, l alkyl esters of (meth)acrylic acids such as hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, lauryl methacrylate: glycidyl acrylate, glycidyl methacrylate: methoxybutyl acrylate, methoxybutyl methacrylate, acrylic C2 of (meth)acrylic acid such as methoxyethyl acid, methoxyethyl methacrylate, ethoxybutyl acrylate, and ethoxybutyl methacrylate
~11 alkoxyalkyl ester: 0 of (meth)acrylic acid such as allyl acrylate and allyl methacrylate
2 to 3 alkenyl esters: 02 to 8 hydroxyalkyl esters of (meth)acrylic acid such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypubil acrylate, hydroxypropyl methacrylate: dimethylamine, noethyl acrylate,
Aminoalkyl esters of (meth)acrylic acid such as diethylaminoethyl acrylate, dimethylaminoethyl methacrylate, and diethylaminoethyl methacrylate: acrylamide, methacrylamide: acrylic acid, methacrylic acid.

Furthermore, the above acrylic unsaturation 1 [non-resting unsaturation'lt
As a single unit, styrene, α-methylstyrene, vinyltoluene, acrylonitrile, vinyl acetate, vinyl propionate, vinyltriethoxysilane, vinyltris (β
(methoxyethoxy)silane, (meth)acrylates containing alkoxysilyl groups such as γ-methacryloxypropyltrimethoxysilane, 2-perfluoroisononylethyl methacrylate, 2-barfluorononylethyl methacrylate, 2-perfluoro Examples include (meth)acrylates containing perfluoroalkyl groups such as isononylnigel acrylate and 2-perfluorodecylethyl methacrylate, methacrylic nitriles, acrolein, methacrolein, butadiene, isoprene, etc. It is used by appropriately copolymerizing with the above-mentioned acrylic monomer depending on the desired physical properties.

The organopolysiloxane modified copolymer that is the object of the present invention has a number average molecular weight of about 3.000 to about 100.000.
, preferably in the range of about to, ooo to about 45,000, and has a glass transition temperature of 140 to 80
℃, preferably in the range of -20 to 50℃.

One thiol group used in the present invention is attached to the terminal or side chain.
Typical examples of organopolysiloxanes containing more than 100% siloxane are listed below (in the margin below).

Other examples include polythiol compounds obtained by reacting epoxy-modified silicones with polyvalent thiol compounds such as neopentyl glycol tetrathioglycolate or thiopropionate. 0.01 to 50 parts by weight, preferably 0.1 to 3 parts by weight, based on the abrasive part
It is best to choose λ within the range of 0 parts by weight.

Furthermore, an organopolysiloxane-modified copolymer containing an organopolysiloxane compound according to the present invention can be synthesized according to the following procedure.

That is, a predetermined proportion of an organopolysiloxane compound containing one or more thiol groups at the terminal or side chain is blended with the above-mentioned ethylenically unsaturated 'tff, and if these are required, the presence of a radical polymerization initiator is required, and normal conditions are applied. Combine with heat or light according to the instructions. This polymerization may be carried out by either solvent-free polymerization or solution polymerization, but in the case of organopolysiloxane compounds containing alkoxysilyl groups, emulsion polymerization or suspension polymerization is not preferred because the alkoxysilyl groups may be hydrolyzed. .

The above radical polymerization initiator is usually used in an amount of 0.005 to 3 parts by weight per 1 lt part of ethylenically unsaturated initiator. Nitrile (AIBN), 2.2
Examples include °-azobisisovaleronitrile, 2.2°-azobis(2,4-dimethylvaleronitrile), benzoyl peroxide (BPO), and t-butyl peroxide. In addition, in the case of photopolymerization, the radical polymerization initiator may or may not be used.

The organopolysiloxane-modified copolymer produced as described above (!) has a surface-migration property of the organopolysiloxane group, so even the introduction of a small amount of the organopolysiloxane group has the effect of modifying the surface or interface (for example, anti-fouling effect). can demonstrate. Further, its uses include water repellent agents for textiles, adhesion agents (particularly for glass surfaces), anti-icing, anti-sticking agents, and base resins for weather-resistant additives.

Next, the present invention will be specifically explained with reference to Examples.

(Example 1) 180 g of toluene was charged into a II2 separable flask equipped with a stirrer, a dropping funnel, a thermometer, a nitrogen inlet tube, and a condenser with a calcium chloride tube, and heated while introducing nitrogen gas. 3 after the liquid temperature reaches the boiling point of toluene and begins to reflux.
After purging the system with nitrogen for 0 minutes, 215 g of methyl methacrylate was added.

2-ethylhexyl acrylate 40g, styrene 54g
g, Plaxel FM-184g (manufactured by Daicel Chemical Co., Ltd., ε
- caprolactone modified hydroxyethyl methacrylate), methacrylic a 3g, toluene 100g, X-22
-9804g (manufactured by Etsu Kagaku Co., Ltd., mercapto-modified silicone oil 9 A mixed solution consisting of 2g of azobisisobutyronitrile (AIBN) was added dropwise over 3 hours.After the completion of 6 drops, thermal formation was carried out for 1 hour. After that, add 5 g of AIBNl and 30 g of toluene.
After completing the 7 additions, which were divided into 6 times and confirmed every 10 minutes,
After aging for 1 hour, 90 g of toluene and 29.4 g of a 50% toluene solution of Plaxel 208 (manufactured by Daicel Chemical Co., Ltd., Polycab[I Lactodiol) as a polymer modifier.
was added, and then cooled to room temperature. Then 3.5 g of triethylamine was added. Non-volatile content 50.3%, G P
The average molecular weight measured by C was 15.500.

(Examples 2 to 5, Comparative Example) Lamination was carried out under the same conditions as in Example 1 using the formulations shown in F below.

(The following is a blank space) [Test] The surface migration properties of the organopolysiloxane-modified copolymers and copolymers of ethylenically unsaturated monomers obtained in Examples 1 to 5 and Comparative Example 2 were tested.

The slope used in the test was adjusted as follows. To 100 parts by weight of the polymer solutions of Examples and Comparative Examples, 15 parts of hexamethylene diisocyanate trimer (Coronate EH, manufactured by Nippon Polyurethane Co., Ltd.) was added and mixed to prepare a coating liquid. , Spread the second solution on an aluminum plate and a transparent glass plate, and place it in a constant temperature room (25℃, 6℃).
5%) for one week.

(1) Adhere 18 mm width made by Chiban to cellophane tape to an aluminum plate with a peel strength of F, and roll it back and forth 5 times with a 1 kg roller at a crosshead speed of 300 mm/min for 20 minutes! An 80° peel test was conducted.

(2) Spread 0.5 liters of ion-exchanged water on the coating film of the glass plate above.
g was placed quietly, and the area of the water droplet was measured.

(The following is a blank space) [Effects of the invention] The novel graft copolymer of the present invention has excellent water repellency, stain resistance, and weather resistance, and can be used as a water repellent agent for textiles, a waterproofing agent, a blue waterproof paint, and a paper lining. Useful as a base resin for sprays and weather-resistant paints.

Patent applicant: Showa Kobunshi Co., Ltd.

Claims (1)

[Claims] One or more ethylenically unsaturated monomers,
The amount of organopolysiloxane compound containing one or more thiol groups is 0.01 to 5 per 100 parts by weight of the monomer.
A method for producing an organopolysiloxane-modified copolymer, which comprises polymerizing in the presence of 0 parts by weight.