JPH10237176A - Silicone-based polymer and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a copolymer consisting of a saturated hydrocarbon-based polymer segment and a silicone-based polymer segment, and improved in coatability without significantly lowering its weathering resistance and mechanical properties. SOLUTION: This copolymer is obtained by reacting (A) a saturated hydrocarbon-based polymer component, preferably a polymer component having an alkenyl or vinyl group with (B) a silicone-based polymer component, wherein the component B is a silicone-based polymer having a hydrosilyl group, preferably a polymer shown by the formula (R is a 1-20C monovalent organic group; (n) is an integer of 2 or more; (w) is the number of cyclic structures in the silicone-based polymer; (x) and (y) are each 2 or more, but (x)+(y)=2(n)+2-2(w)).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a copolymer comprising a saturated hydrocarbon polymer component and a silicone polymer component.

[0002]

2. Description of the Related Art Silicone polymers are widely used as raw materials for sealing materials, coating materials and the like because of their excellent weather resistance and mechanical properties. However, since the coating properties of silicone polymers are generally not so good, silicone sealing materials and the like are not used in areas requiring coating.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to improve the coatability of a silicone polymer without significantly deteriorating weather resistance and mechanical properties.

[0004]

The object of the present invention is attained by a copolymer comprising a silicone polymer component and a saturated hydrocarbon polymer component. Further, the present invention provides a copolymer obtained by reacting a saturated hydrocarbon polymer having an alkenyl group with a silicone polymer having a hydrosilyl group, a saturated hydrocarbon polymer having a vinyl group at a terminal, and a hydrosilyl group. And a copolymer obtained by reaction with a silicone polymer having The present invention also provides
Silicone polymer having a hydrosilyl group has the formula (1): in _{Si n O n-1 + w} R x H y (1) [wherein, R same or different monovalent organic group having 1 to 20 carbon atoms N is an integer of 2 or more, w is the number of cyclic structures in the silicone polymer, x and y are each an integer of 0 or more, provided that x + y = 2n + 2-2w]. To the above copolymer.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The silicone polymer component in the copolymer of the present invention means a polymer component having a polysiloxane main chain skeleton, and the number average molecular weight (GPC method, (Polystyrene equivalent) 300 ~
It is preferably about 400,000.

In the copolymer of the present invention, the saturated hydrocarbon-based polymer component means a polymer component which does not substantially contain a carbon-carbon unsaturated bond other than an aromatic ring in a main chain. The number average molecular weight (GPC method, converted into polystyrene) of the hydrocarbon polymer is preferably about 300 to 100,000. The saturated hydrocarbon polymer component has excellent weather resistance, and does not lower the weather resistance of the silicone polymer component.

[0007] The copolymer of the present invention is a conventionally known copolymer such as a block copolymer and a graft copolymer. The number average molecular weight (GPC method, calculated as polystyrene) of the copolymer of the present invention is preferably about 500 to 500,000, and particularly preferably about 1,000 to 300,000. The copolymer of the present invention can be produced using a silicone polymer and a saturated hydrocarbon polymer as raw materials.
For example, it can be obtained by reacting a saturated hydrocarbon polymer having an alkenyl group with a silicone polymer having a hydrosilyl group.

[0008] The silicone polymer refers to a polymer having a polysiloxane main chain skeleton, and the silicone polymer having a hydrosilyl group refers to a silicone polymer having at least one hydrosilyl group in a molecule. Refers to union. Here, one hydrosilyl group refers to one SiH group. Therefore, when two hydrogen atoms are bonded to the same Si, two hydrosilyl groups are used.

[0009] Examples of the silicone-based polymer having a hydrosilyl group, the formula _{(1): Si n O n} -1 + w R x H y (1) wherein, R represents a monovalent C1-20 N may be the same or different in the organic groups, n is an integer of 2 or more, w is the number of cyclic structures in the silicone polymer, x and y are each an integer of 0 or more, provided that x + y = 2n + 2-2w]. To be used. Examples of R in the formula (1) include hydrocarbon groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a phenyl group, a 2-phenylethyl group, and a 2-methyl-2-phenylethyl group. Is a methyl group, a phenyl group, a 2-phenylethyl group, a 2-methyl-
A 2-phenylethyl group is preferred.

Specific examples of the silicone polymer having a hydrosilyl group are as follows.

[0011]

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A chain or cyclic compound represented by the formula: Number average molecular weight (GPC) of the silicone polymer
(In terms of polystyrene conversion) is preferably about 300 to 400,000, more preferably about 1,000 to 200,000. In the present invention, the number of hydrosilyl groups contained in the silicone polymer having a hydrosilyl group may be one or more, but is preferably 1 to 10.

In the present invention, the term "saturated hydrocarbon polymer" is a concept meaning a polymer which does not substantially contain a carbon-carbon unsaturated bond other than an aromatic ring in the main chain, and constitutes the main chain. It means that the repeating unit is composed of a saturated hydrocarbon. The main chain of the saturated hydrocarbon polymer is
Indicates the portion of the polymer excluding the molecular chain terminals or side chains.
Therefore, in the present invention, even if it has an alkenyl group at the molecular terminal or side chain, a saturated hydrocarbon polymer as long as it does not have a carbon-carbon double bond other than the terminal or side chain except an aromatic ring Becomes An alkenyl group refers to a carbon atom active in a hydrosilylation reaction.
A group having a carbon double bond. Examples of the alkenyl group include, for example, a vinyl group, an allyl group, a methylvinyl group, a propenyl group, a butenyl group, a pentenyl group, an aliphatic unsaturated hydrocarbon group such as a hexenyl group, a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, and a cyclohexenyl group. Examples include a cyclic unsaturated hydrocarbon group such as a group, and a vinyl group and an allyl group are particularly preferable. In the present invention, the saturated hydrocarbon polymer preferably has 1 to 10 alkenyl groups at molecular terminals or side chains. The saturated hydrocarbon polymer is obtained by (1) polymerizing an olefinic compound having 1 to 6 carbon atoms such as ethylene, propylene, 1-butene, isobutylene or the like as a main monomer; (2) diene-based polymer such as butadiene or isoprene; It can be obtained by methods such as homopolymerizing the compound or copolymerizing the olefin compound and the diene compound and then hydrogenating, but it is easy to introduce a functional group into the terminal and easy to control the molecular weight. From the viewpoint that the number of terminal functional groups can be increased, an isobutylene-based polymer, a hydrogenated polybutadiene-based polymer, or a hydrogenated polyisoprene-based polymer is preferable.

In the isobutylene-based polymer, all of the monomer units may be formed from isobutylene units, and the monomer unit having copolymerizability with isobutylene is preferably 50% ( % By weight, the same applies hereinafter), more preferably 30% or less, particularly preferably 20% or less. Examples of such a monomer component include olefins having 4 to 12 carbon atoms,
Examples thereof include vinyl ethers, aromatic vinyl compounds, vinyl silanes, allyl silanes, and the like. Specific examples of such a copolymer component include, for example, 1-butene, 2-butene, 2-methyl-1-butene, 3-methyl-1-butene, pentene, 4-methyl-1-pentene, hexene,
Vinylcyclohexane, methylvinyl ether, ethylvinyl ether, isobutylvinyl ether, styrene, α-methylstyrene, dimethylstyrene, pt-
Butoxystyrene, p-hexenyloxystyrene, p
-Allyloxystyrene, p-hydroxystyrene, β-
Pinene, indene, vinyldimethylmethoxysilane, vinyltrimethylsilane, divinyldimethoxysilane, divinyldimethylsilane, 1,3-divinyl-1,1,1
3,3-tetramethyldisiloxane, trivinylmethylsilane, tetravinylsilane, allyldimethylmethoxysilane, allyltrimethylsilane, diallylmethoxysilane, diallyldimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylmethyldimethoxy Examples include silane.

[0015] In the hydrogenated polybutadiene-based polymer and other saturated hydrocarbon-based polymers, similarly to the case of the isobutylene-based polymer, in addition to the monomer unit as a main component,
Other monomer units may be contained. Further, in the saturated hydrocarbon polymer, butadiene, isoprene, 1,13-tetradecadiene, as long as the object of the present invention is achieved,
A small amount, preferably 10% or less, of a monomer unit such as a polyene compound such as 1,9-decadiene or 1,5-hexadiene, in which a double bond remains after polymerization, may be contained.

The number average molecular weight (GPC method, in terms of polystyrene) of the saturated hydrocarbon polymer, preferably isobutylene polymer, hydrogenated polyisoprene or hydrogenated polybutadiene polymer is preferably about 300 to 100,000. In particular, a liquid material having a flow rate of about 1,000 to 40,000 and a fluid substance are preferable from the viewpoint of easy handling.

The method for producing the saturated hydrocarbon polymer is described in JP-A-8-53514 and JP-A-6-291.
935 and JP-A-6-287241. When reacting a saturated hydrocarbon polymer having an alkenyl group with a silicone polymer having a hydrosilyl group, the ratio of the alkenyl group to the hydrosilyl group is preferably 0.2 to 5.0, and more preferably 0.4 to 2.0. 5
Is more preferred. When this reaction is used, it is possible to obtain a copolymer having a hydrosilyl group or an alkenyl group at a terminal or the like. For example, in the reaction between a silicone polymer and a saturated hydrocarbon polymer, when the molar number of hydrosilyl groups / the molar number of alkenyl groups> 1, a copolymer having a terminal hydrosilyl group can be obtained. A cured product of a copolymer having a hydrosilyl group at a terminal can be obtained by a hydrosilylation reaction with a compound or a polymer having a plurality of alkenyl groups.

When the number of moles of hydrosilyl groups / the number of moles of alkenyl groups <1, a copolymer having an alkenyl group at a terminal or the like can be obtained. A cured product of the copolymer having an alkenyl group at the terminal or the like can be obtained by performing a hydrosilylation reaction with a compound or a polymer having a plurality of hydrosilyl groups. In the present invention, the molecular weight of the copolymer can be arbitrarily set by adjusting the value of the number of moles of the hydrosilyl group / the number of moles of the alkenyl group. When the number of moles of the hydrosilyl group / the number of moles of the alkenyl group = 1, a copolymer having a theoretically infinitely large molecular weight can be obtained.

Saturated hydrocarbon polymerization having alkenyl group
Between the polymer and the silicone polymer having a hydrosilyl group
In the reaction, a hydrosilylation catalyst may be used.
No. There is no particular limitation on the hydrosilylation catalyst,
Conventionally known ones can be used. To give a concrete example, salt
Platinized acid, simple substance of platinum, alumina, silica, carbon
Solid platinum supported on a carrier such as a rack; platinum-bi
Nylsiloxane complex {for example, Pt_n(ViMe_TwoSiO
SiMe_TwoVi)_n, Pt [(MeViSiO) _Four]_m｝;
Platinum-phosphine complex {for example, Pt (PPh_Three)_Four, P
t (PBu_Three)_Four白金; Platinum-phosphite complex ｛For example,
Pt [P (OPh)_Three]_Four, Pt [P (OBu)_Three]_Four(formula
Medium, Me is a methyl group, Bu is a butyl group, Vi is vinyl
Group, Ph represents a phenyl group, n and m represent integers),
Pt (acac)_TwoAlso, Ashby
U.S. Pat. Nos. 3,159,601 and 3,159,662
Platinum-hydrocarbon composites described herein, and Ramolo
-(Lamoreaux) U.S. Pat. No. 3,220,972
The platinum alcoholate catalyst described in the specification is also cited.
Can be

Examples of catalysts other than platinum compounds include
Is RhCl (PPh_Three)_Three, RhCl _Three, Rh / Al_TwoO
_Three, RuCl_Three, IrCl_Three, FeCl_Three, AlCl_Three, P
dCl_Two・ 2H_TwoO, NiCl_Two, TiCl_Four, Etc.
It is. These catalysts may be used alone or in combination of two or more.
You may use together. From the viewpoint of catalytic activity, chloroplatinic acid, platinum-
Olefin complex, platinum-vinylsiloxane complex, Pt
(Acac)_TwoAre preferred. The amount of catalyst is particularly limited
Alkenyl group in a saturated hydrocarbon polymer
10 for ol^-1-10^-8Use in the mol range
Good. Preferably 10^-2-10^-6Use in mol range
Is good. Also, hydrosilylation catalysts are generally expensive.
It is corrosive and generates a large amount of hydrogen gas, causing
May be foamed.^-1Do not use more than mole
Better.

The copolymer produced in the present invention is preferably, for example, a block copolymer or a graft copolymer, but the structure is not particularly limited, and any conventionally known copolymer can be produced arbitrarily. It is possible. The copolymer of the present invention may be used for various applications as it is, but if necessary, may be used as a curable composition capable of vulcanization or cross-linking reaction. When a curable composition is used, the composition can be cured by a usual method for curing a silicone polymer.
Methods for obtaining a cured product include (1) vulcanization using, for example, sulfur or peroxide, and (2) a copolymer or a polymer having a plurality of alkenyl groups with a copolymer having a hydrosilyl group at a terminal or the like. A curing reaction by a hydrosilylation reaction, and (3) a curing reaction by a hydrosilylation reaction between a copolymer having an alkenyl group at a terminal or the like and an arbitrary compound or polymer having a plurality of hydrosilyl groups, include but are not limited to these. It is not something to be done.

The copolymer of the present invention or a cured product thereof is
Sealing materials, coating materials, various molded products, sealing materials,
It can be suitably used for applications such as electric insulating materials, adhesives, pressure-sensitive adhesives, paints, vibration damping materials, potting materials, medical rubber, sealing materials for construction, sealing materials for double glazing, and the like. As a paint for coating the copolymer of the present invention, for example, oil-based paint, water-based paint, lacquer, varnish, enamel, curable or non-curable paint such as rubber-based paint can be used, for example, acrylic System, alkyd system, polyester system, epoxy system, phenol resin system, acryl silicone system paint, etc. can be used.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

[0024]

【Example】

Example 1 Polymer A having the following structure and synthesized in a 30 ml reaction flask by the method described in JP-A-8-53514
(Analytical values are shown in Table 1) 5.49 g (vinyl group content 2.0
2 mmol), polymer B (analytical values are shown in Table 1), 3.
98 g (Si-H group content 1.01 mmol) and 5 ml of heptane were added.

As a catalyst, bis (1,3-divinyl-1,1,3,3-tetramethyldisiloxane) platinum complex catalyst (8.3 × 10 ⁻⁵ mmol / μl, xylene solution) 4.9 μl (weight) After uniformly mixing the amount of platinum with respect to the number of moles of the vinyl group in the combined A: 5 × 10 ⁻⁴ equivalent),
Stirred at C for 6 hours. Thereafter, volatiles were distilled off under reduced pressure to isolate 9.2 g of the block copolymer, and its properties were evaluated by GPC and 1H-NMR. Table 2 shows the results.

Example 2 A polyorganohydrogensiloxane and a platinum-based catalyst were added to the block copolymer obtained in Example 1, mixed, and then heated to prepare a cured product. When an aqueous acrylic paint was applied to the cured product, the coatability of the block copolymer was better than that of the silicone polymer.

[0027]

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[0028]

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[0029]

[Table 1]

[0030]

[Table 2]

[0031]

According to the method of the present invention, it is possible to obtain a resin having improved coatability of a silicone polymer.

Claims (5)

[Claims] 1. A copolymer comprising a saturated hydrocarbon polymer component and a silicone polymer component. 2. The copolymer according to claim 1, which is obtained by reacting a saturated hydrocarbon polymer having an alkenyl group with a silicone polymer having a hydrosilyl group. 3. The copolymer according to claim 1, which is obtained by reacting a saturated hydrocarbon polymer having a vinyl group at a terminal with a silicone polymer having a hydrosilyl group. 4. A silicone polymer having a hydrosilyl group represented by the formula (1): Si _n O _{n-1 + w} R _x H _y (1) wherein R is a monovalent C 1-20 carbon atom. N may be the same or different in the organic groups, n is an integer of 2 or more, w is the number of cyclic structures in the silicone polymer, x and y are each an integer of 0 or more, provided that x + y = 2n + 2-2w]. The copolymer according to claim 1, wherein the copolymer is produced. 5. A method of coating a coating on the surface of a silicone polymer or a cured product using the silicone polymer, wherein the polymer comprises a saturated hydrocarbon polymer component and a silicone polymer component. A coating method using a coalesced product or a cured product using the copolymer.