JPS60184513A - Production of graft polymer - Google Patents

Abstract

PURPOSE:To produce a graft polymer excellent in water repellency and oil repellency and good in compatibility with solvents, by grafting a perfluoroalkyl group-containing alkyl(meth)acrylate onto an alkyl(meth)acrylate polymer. CONSTITUTION:0.01-50pts.wt. perfluoroalkyl group-containing (meth)acrylate (e.g., heptadecafluorononyl 2-methyl-2-propenoate) is grafted onto 100pts.wt. polymer (viscosity as measured in a 40% toluene solution at 30 deg.C of about 200- 2,000cP) based on an alkyl(meth)acrylate (where the alkyl group is 16C or lower) at 50-140 deg.C in an inert organic solvent (e.g., toluene) in the presence of about 0.005-5pts.wt. polymerization initiator (e.g., azobisisobutyronitrile).

Description

DETAILED DESCRIPTION OF THE INVENTION [I] Object of the Invention The present invention relates to a method for producing a graph I polymer suitable for use in paints with excellent water testability and durability.

More specifically, an acrylate or methacrylate having a perfluoroalkyl group is added to a polymer mainly composed of alkyl acrylate or methacrylate-1 in an inert organic solvent at a temperature of 50 to 140°C in the presence of a polymerization initiator. The present invention relates to a method for producing a graft polymer characterized by polymerization, and the object thereof is to provide a graft polymer that has excellent Matsumoto properties and is suitable for use in paints.

[II] Background of the Invention Undersea structures such as the bottoms of ships, tanks, buoys, and water pipes of thermal power plants are home to a large number of plants and animals, such as Fujibo, oysters, serpura, blue laver, and Ulva, which cause various damage to them. is bringing about. For example, in the case of a ship, the growth of barnacles and sea lettuce on the bottom of the ship increases the resistance of the ship, which increases the amount of fuel used during service. Conventionally, antifouling paints containing cuprous oxide, organic tin compounds, etc., which are harmful to humans and animals, have been used to prevent these damages. The substances contained in such an antifouling paint diffuse or elute into seawater, thereby preventing animals and plants from adhering to the coated object. However, the antifouling validity period of such antifouling paints is usually only two years at most! It only has a year mark and must be repainted each time to prevent damage from animals and plants in the sea. Furthermore, since this antifouling paint contains the above-mentioned toxic substances, there are problems in terms of safety and health on the painted surface.

It is said that attached animals and plants in seawater produce sticky secretions, which act as adhesives and adhere to the surfaces of the underwater structures such as the bottoms of ships and grow.

Therefore, in addition to the above-mentioned method of using toxic substances, if the surface of the underwater structure to be antifouled is coated with a surface that does not attract substances secreted by animals and plants, it is basically possible to prevent these animals and plants from adhering to it. Conceivable. In this regard, compounds with perfluoroalkyl groups in their molecules have extremely low surface energy, and surfaces made of compounds with low surface energy have poor stickiness, so they can be used in antifouling paints. Taking advantage of the property of having a low surface due to perfluoroalkyl groups, fluorine-containing polymers with perfluoroalkyl group-containing side chains are used as water testing oil agents for textile fabrics, etc. , perfluoroalkyl group-containing side chains, carboxyl groups, methylol groups,
Thermosetting resins containing functional groups such as hydroxyl groups, epoxy groups, and amide-aldehyde reactive groups have been proposed. Furthermore, in order to achieve compatibility with other resins, fluorine-containing polymers with perfluoroalkyl group-containing side chains are randomly copolymerized with aromatic copolymer components to form coatings such as paints and coating materials. It is known that it can be mixed into materials to impart oil-like properties to coatings and improve weather resistance.

For these reasons, it is considered that fluorine-containing polymers having perfluoroalkyl groups can be used as antifouling paints. Although it is effective to incorporate such a fluorine-containing polymer having a perfluoroalkyl group into a coating film that requires oil-based and antifouling properties, perfluorinated polymers such as those already proposed are effective. In the case of alkyl group-containing side chains and other random covalent polymers, the compatibility with the coating film-forming resin base silver has not yet been resolved. In addition, heat curing is required to maintain adhesion to the group surface, so the process requires curing at a high temperature of 17X. There's a problem.

Furthermore, the effects of conventionally proposed fluorine-containing copolymers having perfluoroalkyl group-containing side chains cannot be seen unless the fluorine content is increased.

[111] Structure of the Invention Based on the second point, the present inventors have developed a coating film-forming resin that has excellent oil and water handling properties. (As a result of various searches for obtaining resins (polymers) that are promising as raw materials for paints that have excellent compatibility with materials, antifouling properties, hygienic properties, and sustainability, we found that [the number of carbon atoms in the alkyl group is at most 16]) Polymers containing 0.01 to 50 parts by weight of perfluoroalkyl groups per 100 parts of polymer (hereinafter referred to as ``(meth)acrylate ff1 polymers'') acrylate) or methacrylate (hereinafter referred to as "fluorine-containing monomer") in the presence of a polymerization initiator in an inert organic solvent at a temperature of 50 to 140°C. It is a promising resin as a raw material for paints that does not have the above-mentioned drawbacks, has good proofreading properties, and has excellent compatibility with film-forming resins, antifouling properties, hygiene properties, and sustainability. We discovered something and arrived at the present invention.

[IV] Effects of the Invention The pure polymer obtained by the present invention, including its manufacturing method, exhibits the following effects.

(1) A small amount of the graph of the present invention) ・It is possible to coat objects by mixing them with paint such as acrylic paint or urethane paint.
Since the surface of the material can be made to have low surface energy, it is possible to bring about imitability and proofability. therefore,
It is effective as a paint for metal articles, ships, tanks, buoys, and waterway conduit pipes for thermal power plants.

(2) Since it has good compatibility with acrylic paints and urethane paints, even if it is immersed in water for a long time, it will not be eluted into water and its effect can be maintained for a long time.

(3) It does not cause environmental pollution because it does not elute to the outside.

(4) Hygienic.

(5) Excessive water testing, proofing oil, and antifouling effects can be achieved with a small amount of fluorine content.

(8) By performing graft polymerization using a suitable organic solvent, the obtained graft polymer solution can be used as it is.
Not only can it be used as an advantage, but it can also provide water testability to the coating film and reduce the surface energy. The coating film thus obtained has resistance to water-soluble stains and can prevent the spread of water 11k into the coating film.

[V] Light E! Specific Theory of JJ 11 (A) (Meth) Acrylate Polymer The (meth) acrylate polymer used in the present invention is mainly composed of alkyl acrylate or methacrylate in which the alkyl group has at most 16 carbon atoms. It is a polymer as a component. The alkyl group may be straight or branched,
Those having 12 or less carbon atoms are preferred, and those having 8 or less carbon atoms are particularly preferred. Suitable alkyl groups include methyl, propyl, n- or isobutyl, hexyl and octyl. In the present invention, among these (meth)acrylate polymers, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate,
Polymers containing probyl methacrylate-1., butyl acrylate, or 2-ethylhexyl acrylate as a main component (50 mol % or more) are suitable. These (meta)
Acrylate polymers are industrially produced and used in a wide range of fields, and their properties are widely known.In particular, the viscosity of a 40% toluene solution at 3000 °C is 200%. ~200
0 centipoise is desirable.

(B) Fluorine-containing monomer The fluorine-containing monomer used in the present invention is an acrylate or methacrylate having a perfluoroalkyl group, and the terminal group has a general formula of RfQCH2.
It is important to have a side chain that is -. Rf represents a perfluoroalkyl group having 4 to 20 carbon atoms, and may be branched or linear.

When Rf is 3 or less, the obtained graph 1-polymer does not have sufficient water testability. On the other hand, if the number of carbon atoms is 21 or more, it is not only difficult to obtain the 1,000 carbon atoms, but also problems arise in producing a graft polymer.

In particular, those having 6 to 12 carbon atoms are preferred. Q is C
nH2n-, and desirably n is 5 or less. Therefore, the fluorine-containing monomer used in the present invention is preferably one represented by the following formula [(1) Formula 1].

CH2=C-COOCH2QRf (I)CI) In the formula, Rf and Q are the same as above, and R represents a hydrogen atom or a methyl group.

Among the fluorine-containing monomers used in the present invention, preferred representative examples include 3, 3, 4, 4, 5°, 5.
8. II,? ,? , 8, 8, 9. S, 9-hebutadecafluorononyl-2-methyl-2-propenoate, 3,3
,4,4,5,5. θ, 8°7,? ,8,8,9,9,
10,10,11,11,12,12.12-heneicosafluorododecyl-2-propenoate, 3,3,4,
4,5°5.8,6. ? ,,7,3,8,9,8,10
, 10.10-heptadecafluorodecyl-2-propenoate, 3,3,4,4,5,5,6,6,7°7.8
．． 8, 9, 9. 10. 10, 11, 11, 12, +2
．． 13,13.14,14,14-pentacosafluorotetradecyl-2-propenoate and 3,3,4
, 4,5,5,8,6,7,7,8,8.8-tridecafluorobutyl-2-propenoate.

(C) Polymerization conditions In producing the graft polymer of the present invention, the above (
The meth)acrylate polymer and the fluorine-containing monomer may be used alone or in combination of two or more.

The polymerization temperature is 50 to 140°C, preferably 50 to 120°C, and particularly preferably 60 to 120°C. 5
If the graft polymerization is carried out at a temperature below 0°C, it will take a long time to produce the graft polymer, which is industrially undesirable. On the other hand, if the polymerization is carried out at a temperature exceeding 140°C, the polymerization can be completed in a relatively short time, but this is not desirable because the physical properties of the grafted polymer are not good.

In addition, the polymerization time is usually between 15 minutes and C11,
The time is preferably 30 minutes to 5 hours, particularly 30 minutes to 4 hours. Attempting to complete the polymerization in less than 15 minutes requires higher polymerization temperatures and makes it difficult to control the polymerization.

- If the polymerization time exceeds 6 hours, it is easy to control the polymerization, but it is not suitable for industrial use due to the long polymerization time.

The ratio of the fluorine-containing monomer to 100 parts by weight of the (meth)acrylate polymer is 0.01 to 50 parts by weight, preferably 0.02 to 50 parts by weight, particularly 0.
．． 1 to 40 parts by weight is suitable. 100 weight-hj parts (
If the ratio of the fluorophore monomer to the meth)acrylate polymer is less than 0.01 part by weight, it is not preferable because the fJt of the graft polymer will be low in imitability. on the other hand,
When the amount exceeds 50, the graft reactivity decreases and the resulting graft copolymer has poor compatibility with paints.

The graft polymerization of the present invention is carried out in an inert organic solvent in the presence of a polymerization initiator. The polymerization initiator has a half-life of temperature 6.
Preferably, the heating time is 0.5 to 2 hours at 0 to 120°C. Representative examples of such polymerization initiators include azobisisobutyronitrile, benzoyl peroxide, di-tertiary-butyl peroxide, lauryl peroxide, and cumene hydroperoxide. The ratio of the polymerization initiator to 100 parts by weight of the (meth)acrylate polymer is generally 0.005 to 5.0 parts by weight, and 0.005 to 5.0 parts by weight.
0.01 to 5.0 parts by weight are preferred, and 0.01 to 3.0 parts by weight are preferred. The inert organic solvent is one that dissolves the (meth)acrylate polymer, the fluorine-containing monomer, and the polymerization initiator, and is inert.

The inert organic solvent is liquid at normal temperature and pressure,
Those having a boiling point of 50°C to 300°C are preferred.

Typical inert organic solvents include aliphatic or aliphatic hydrocarbons (e.g., pentane, hexane,
heptane, octane, cyclohexane), aromatic hydrocarbons (benzene, toluene, xylene), petroleum ether,
Examples include tetrahydrofuran, 1,4-dioxane, methyl ethyl ketone, methyl chloroform, l-lichloroethylene, tetrachloroethylene, tetrachlorodifluoroethane, trichlorotrifluoroethane, and the like.

The amount of these inert organic solvents is generally 25 ml to 1 fL per 100 g of the (meth)acrylate polymer, and preferably 60 mL to 0.2 mL. 10
The ratio of inert organic solvent used to 0g of (meth)acrylate polymer is 25+n Bunmi II! In 4, (meta)
51f: L is not an undesirable measure because it takes a long time to dissolve the Acrylay-I polymer, and it also has a high viscosity and is used when stirring etc. during graft polymerization.
It becomes.

On the other hand, even if it is used in excess of X, there is a problem because the concentration of simulant and anti-oleaginous properties in the solution decreases.

Other polymerization methods include emulsion polymerization and suspension polymerization, but graft polymers produced by these methods do not provide the expected effects.

[VI] Examples and Comparative Examples The present invention will be explained in more detail with reference to Examples below.

In addition, in the Examples and Comparative Examples, the proofing properties were measured by placing the obtained graft polymer solution on an acrylic plate in m 4i L,
, expressed by the water contact angle of the resulting coating film. Also, apply pine oil in the same way as above! TjL, n- of the resulting coating film
Indicated by the contact angle of hexadecane. In both cases, the larger the contact angle, the greater the imitability or anti-oil resistance. Further, the compatibility is determined by visually observing the obtained graft polymer solution and expressed as follows.

○: Precipitate does not exist in the solution ×: Precipitate exists in the solution Example 1 47; 5 g of polymethyl methacrylate [viscosity of 40% toluene solution at 30°C (the same applies hereinafter) 400 centipoise, hereinafter ""Polymer(A)"], 2.5 g
CH=CHC00CH2CH2C8F17 [hereinafter referred to as "compound (1)"], 0.5 g of benzoyl peroxide and 60 g were placed in a 300 cc flask, and graft polymerization was carried out at a temperature of 80 ° C under a nitrogen atmosphere for 3 hours with stirring. I did this. The graft ratio of the obtained graft polymer was 4.1%.

Example 2 The amount of polymer (A) used in Example 1 was reduced to 45.
Graft polymerization was carried out under the same conditions as in Example 1, except that the amount of compound (1) used was changed to 5.0 g and 5.0 g.

The grafting rate of the obtained graft polymer was 8.4%.Example 3 Instead of the polymer (A) used in Example 2, polyethyl acrylate having the above-mentioned viscosity of 380 (the amount used was Correct matching was performed in the same manner as in Example 1, except that the same graph as in Example 2 was used. The grafting rate of the obtained graft polymer was 7.8%.

Example 4 Instead of the polymer (A) used in Example 2, a cane polymer of methyl methacrylate and ethyl acrylate in which the copolymerization ratio of methyl methacrylate was 80 mol % (the above viscosity was 810 centipoise, the amount used was determined according to the experiment) Graft polymerization was carried out under the same conditions as in Example 2, except that the same polymer as in Example 2 was used. The grafting rate of the obtained kraft polymer was 7.5%.

Comparative Example 1 The amount of polymer (A) used in Example 1 was 30g.
and except that the amount of compound (1) used was changed to 20g,
Graft polymerization was carried out in the same manner as in Example 1. The grafting rate of the obtained graft polymer was 32%. Comparative Example 2 The amount of polymer (A) used in Example 1 was reduced to 49%.
Graft polymerization was carried out under the same conditions as in Example 1, except that the amount of the compound (1) was changed to 99 g and 0.01 g. The grafting rate of the obtained graft polymer was 0.01
It was 5%.

Comparative Example 3 5.0 instead of compound (1) used in Example 1
Graft polymerization was carried out in the same manner as in Example 1, except that CH-CHGOOCH2CO and Cl8F3 were used. The grafting rate of the obtained graft polymer was 3.2%.

The proofreadability and oil resistance of each of the graft polymers thus obtained were measured. The results and the compatibility of the resulting graft polymer solutions are shown in Table 1.

From the results of the Examples and Comparative Examples shown in Table 1, it can be seen that the graft polymer obtained by the present invention not only has excellent proofreadability and anti-oil properties, but also has good compatibility with solutions (toluene). That is clear.

Patent applicant: Showa Denko Co., Ltd. Representative Patent Attorney Sei Kikuchi

Claims (1)

[Claims] 0.01 to 50 parts by weight of acrylate or methacrylate-1 having a perfluoroalkyl group per 100 parts by weight of a polymer whose main component is an alkyl acrylate or methacrylate whose alkyl group has at most 16 carbon atoms. A method for producing a graft polymer, which comprises polymerizing in an inert organic solvent at a temperature of 50 to 140°C in the presence of a polymerization initiator.