JP3393905B2 - Method for producing functional group-containing polymer - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a hydrosilylation reaction between an alkenyl group-containing polymer and a silicon compound.

[0002]

2. Description of the Related Art Conventionally, when an alkenyl group-containing polymer is reacted with a silicon compound, when the alkenyl group-containing polymer is a liquid having a low viscosity at room temperature, the silicon compound and the hydrosilylation are heated. It is mixed with the catalyst without solvent.
When the alkenyl group-containing polymer has a high viscosity at room temperature or is solid due to crystallinity, etc., it is made into a low-viscosity liquid using a non-reactive good solvent and then heated to form a silicon compound. The reaction product is obtained by mixing with a hydrosilylation catalyst, and after the reaction, the solvent is distilled off.

[0003]

However, when the target product thus obtained has a high viscosity or is solid due to crystallinity or the like, it becomes difficult to dispense or transfer it from the reaction vessel, and the product is recovered. There have been problems such as a large decrease in yield and an increase in the load of the washing operation when changing the product type.

[0004] Therefore, in order to solve these problems, devising such as paying out and transferring operation under heating, or while leaving a small amount of solvent left behind, etc. have been devised. Since it is included, the condensation reaction due to heating may proceed, and there remain problems such as quality deterioration and complicated processes. Further, when a solvent is used during the reaction, there is a problem that the equipment becomes large in size because a solvent recovery step is industrially necessary.

[0005]

In view of the present circumstances, the present invention has been studied by the present inventors to solve the above-mentioned problems, and after the inventors of the present invention have diligently studied the functional group-containing weight to be produced in the present invention. When the combination is industrially used, it is rarely used as it is, and in many cases, attention is paid to the fact that it is used as an industrial product after a compounding step such as addition of a plasticizer according to the intended use. As a result, the present invention has been achieved.

That is, the present invention (A) has at least one alkenyl group in one molecule and has an average molecular weight of 50.
A polymer which is 0~200,000, (B) the following formula ^{H - [- Si (-R 1} b) (- X 2-b) -O -] - Si
_{^{(-R 2 a) (- X}} 3-a) [ the alkyl group of the formula, R ¹ and R ² are both 1 to 20 carbon atoms, from 6 to 20 carbon atoms ant - group, having 7 to 20 carbon atoms
Aralkyl group or triorganosiloxy group, and may be the same or different. X is a hydroxyl group or a hydrolyzable group, and when two or more are present, they may be the same or different. a is 0, 1, 2 or 3;
b is 0, 1 or 2, and m is 0 or an integer of 1 to 18. It has been found that the above-mentioned problems can be solved by a method for producing a functional group-containing polymer, which comprises reacting a compound represented by the formula [1] in the presence of a plasticizer.

The present invention will be described more specifically. The component (A) used in the present invention is at least 1 in one molecule.
Having 5 alkenyl groups and an average molecular weight of 5
The polymer having a number of from 00 to 200,000 is not particularly limited as long as it has an alkenyl group having a hydrosilylation activity capable of performing a hydrosilylation reaction with the component (B), and various polymers can be used. it can. The number of alkenyl groups present in one molecule is at least 1.1, and 10.
Those having up to about 0 are preferable. Specifically, the alkenyl group is, for example, a vinyl group, an allyl group or the like, which may be present as an allyl ether group, and may be at the terminal of the molecule or in the molecule.
A polymer having an average molecular weight of 500 to 200,000 can be suitably used, but preferably 1,000 to 10
50,000, particularly preferably 5,000 to 50,
It is 000. The production method is also not particularly limited, and it can be effectively applied to all polymers produced by any production method.

The main chain constituting the polymer of the component (A) of the present invention may be linear or branched and is not particularly limited, but it is formed by polymerization of an unsaturated monomer, particularly unsaturated hydrocarbon. Those that have been processed are preferred. Considering the industrial utility value of the functional group-containing polymer which is the object of the method of the present invention, it is preferable that the main chain is composed of a saturated hydrocarbon in terms of heat resistance and weather resistance. Among them, those whose main chain is composed of polyisobutylene having a repeating unit based on isobutylene, hydrogenated polybutadiene, and hydrogenated polyisoprene are particularly preferable. Since polymers having these main chains have relatively high viscosity at room temperature, they have the above-mentioned problems and can be said to be particularly suitable for achieving the object of the present invention by applying the method of the present invention. .

In particular, when the field of use of the functional group-containing polymer obtained by the method of the present invention is one in which the characteristics of the crosslinked polymer are utilized, the initial weight of the polymer is controlled to control the physical properties after crosslinking. Since the desired physical properties (high elongation etc.) may be exhibited by shifting the combined molecular weight to the higher molecular weight side, the viscosity of the initial polymer may further increase. In such a case, the effect of the present invention becomes more remarkable.

The silicon-containing compound as the component (B) used in the present invention is represented by the following formula. ^{H - [- Si (-R 1} b) (- X 2-b) -O -] - Si
_{^{(-R 2 a) (- X}} 3-a) wherein the alkyl group of R ¹ and R ² are both carbon atoms of 1 to 20, from 6 to 20 carbon atoms ant - group, having 7 to 20 carbon atoms It is an aralkyl group or a triorganosiloxy group and may be the same or different. This triorganosiloxy group is represented by the formula (R ′) ₃ SiO—, and R ′ is a hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different. X is a hydroxyl group or a hydrolyzable group, and 2
When there are two or more, they may be the same or different. This hydrolyzable group is a halogen, an alkoxy group, an acyloxy group, a ketoximate group, an alkenyloxy group or the like. a is 0, 1, 2 or 3, b is 0, 1 or 2, and m is 0 or an integer of 1 to 18.

Specific examples of the silicon-containing compound include halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane and trimethylsiloxydichlorosilane; trimethoxysilane, triethoxysilane and methyldimethoxy. Silane, dimethylmethoxysilane, phenyldimethoxysilane, 1,
Alkoxysilanes such as 3,3,5,5,7,7-heptamethyl-1,1-dimethoxytetrasiloxane; Acyloxysilanes such as methyldiacetoxysilane and trimethylsiloxymethylacetoxysilane; Bis (dimethylketoximate )
Methylsilane, bis (cyclohexyl ketoximate)
Ketoxymate silanes such as methylsilane and bis (diethylketoximate) trimethylsiloxysilane; dimethylsilane, trimethylsiloxymethylsilane, 1,1,3,
Hydrosilanes having two or more SiH bonds in the molecule such as 3-tetramethyldisiloxane and 1,3,5-trimethylcyclotrisiloxane; alkenyloxysilanes such as methyldi (isopropenyloxy) silane However, the present invention is not limited to these.

Among these compounds, chlorosilanes such as trichlorosilane and methyldichlorosilane, which have high activity in hydrosilylation reaction, are preferable, and from the viewpoint that the obtained functional group-containing polymer has mild hydrolyzability. , And alkoxysilanes such as trimethoxysilane and methyldimethoxysilane are preferable.

When the above-mentioned hydrosilanes having two or more SiH bonds in the molecule are used, it is possible to control the increase in the molecular weight by doubling the molecular weight of the component (A) by three times depending on the amount used. It is preferable from the viewpoint of making it possible.

When reacting the component (A) and the component (B) of the present invention, it is preferable to use a hydrosilylation catalyst. The hydrosilylation catalyst may be any one,
All known materials can be preferably used. Specifically, for example, a simple substance of platinum, a substance such as alumina, silica, carbon black, and the like on which solid platinum is supported, chloroplatinic acid, a complex of chloroplatinic acid with an alcohol, an aldehyde, a ketone, or a platinum-olefin. Complex (for example, Pt (CH ₂ = C
_{H 2) 2 (PPh 3)} 2 Pt (CH 2 = CH 2) 2 Cl
₂ ); platinum-vinylsiloxane complex (for example, Pt _n
(ViMe ₂ SiOSiMe ₂ Vi) _m , Pt [(Me
ViSiO) _{4] m);} platinum - phosphine complex _{(e.g., Pt (PPh 3) 4,} Pt (PBu 3) 4); platinum - phosphite complex _{(e.g., Pt [P (OPh) 3} ]
₄ ), [in the formula, Me is a methyl group, Bu is a butyl group, and Vi is
Is a vinyl group, Ph is a phenyl group, m and n are integers], dicarbonyldichloroplatinum, and Ashby (A
shby) U.S. Pat. Nos. 3,159,601 and 3,159,662, and platinum-hydrocarbon composites, and Lamorrow.
Also included are the platinum alcoholate catalysts described in (Lamoreaux) U.S. Pat. No. 3,220,972. Additionally, the platinum chloride-olefin composites described in Modic US Pat. No. 3,516,946 are also useful in the present invention.

Examples of catalysts other than platinum compounds include RhCl (PPh ₃ ) ₃ , RhCl ₃ and Rh / Al.
₂ O ₃ , RuCl ₃ , IrCl ₃ , FeCl ₃ , AlC
l ₃ , PdCl ₂ · 2H ₂ O, NiCl ₂ , TiCl ₄
Etc.

These catalysts may be used alone or 2
It is also possible to use together more than one species. From the viewpoint of catalytic activity, chloroplatinic acid, a platinum-olefin complex, a platinum-acetylacetonate complex, and a platinum-vinylsiloxane complex are preferable.

The amount of this catalyst is not particularly limited, but it is 10 with respect to 1 mol of the alkenyl group in the component (A).
It is preferably used in the range of ^-1 to 10 ^-8 mol. Preferably 1
It is preferably used in the range of 0 ^-3 to 10 ^-6 mol. If it is less than 10 ^-8 mol, hydrosilylation may not proceed sufficiently. Further, the hydrosilylation catalyst is generally expensive and corrosive, and since hydrogen gas may be generated in a large amount and the cured product may foam, it is better not to use 10 ^-1 mol or more.

The plasticizer used in the present invention has good compatibility with the component (A) polymer, has a relatively high boiling point, and does not inhibit the hydrosilylation reaction. There is no particular limitation as long as it satisfies.

For example, when the main chain of the polymer of the component (A) is composed of saturated hydrocarbon such as polyisobutylene, hydrogenated polybutadiene, hydrogenated polyisoprene, polybutene, hydrogenated polybutene, α- Hydrocarbon compounds such as methylstyrene oligomer, biphenyl, triphenyl, triaryldimethane, alkylenetriphenyl, liquid polybutadiene, hydrogenated liquid polybutadiene, alkyldiphenyl; BAA-15 (Dahachi Kagaku), P-103,
Adipic acid ester compounds such as W320 (Dainippon Ink) and PN-150 (Adeka Argus); TOTM, T
Trimellitic acid ester compounds such as ITM (New Japan Rika), W-700 (Dainippon Ink); NS-100, N
Petroleum-based process oils such as M-26, NP-24, PS-32 (Idemitsu Kosan); Alken-68 (Nippon Petroleum Detergent), BF-1000 (Adeka Argus), KE-82
8 (Arakawa Kagaku), DOTP (New Japan Rika), etc. are preferable, and Alkene-68, PS-
32, DOTP, NS-100, TOTM and the like are particularly preferable, but not limited thereto. In particular,
If the main chain of the polymer constituting the component (A) changes, the kind of plasticizer that is naturally and suitably used will also change accordingly, based on the selection criteria described above.

The amount of these plasticizers used is appropriately determined on the basis of the effect of lowering the viscosity and the total amount of plasticizers used for the intended use of the functional group-containing polymer. For example, about 10 to 100 parts by weight is preferable with respect to the component (A) polymer.

The functional group-containing polymer obtained by the present invention is used as a raw material for, for example, an adhesive, a pressure-sensitive adhesive, a coating material, a sealing material, a waterproof material, a molding material, a cast rubber material, and a spraying material.

[0022]

EXAMPLES Next, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto. Example 1 10 g of an isobutylene polymer having a vinyl group introduced into both ends at a ratio of about 90% and a molecular weight of about 8,000, and a plasticizer PS-32 (produced by Idemitsu Kosan, petroleum-based process oils)
Was weighed in a four-necked flask and heated and mixed at about 65 ° C. to obtain a uniform solution.

Next, in a nitrogen atmosphere, 360 mg of methyldimethoxysilane was added, and after mixing, a platinum-vinylsiloxane complex solution (xylene solution: 8.3 × 10 ⁻⁵ mm in terms of Pt) was added.
ol / μL: Pt _n (ViMe ₂ SiOSiMe ₂ Vi)
_m ) was added thereto, and the mixture was heated and mixed at about 65 ° C., and sampled with the passage of time to perform H-NMR / FT-IR.
By performing the measurement, the reaction rate of hydrosilylation was calculated from the rate of vinyl group disappearance. The results are shown in Table 1. The viscosities after concentration shown in Table 1 are obtained by measuring the viscosities at normal temperature after cooling under reduced pressure at 80 ° C. for 1 hour. Examples 2 to 4, as shown in Table 1, TOTM (Nippon Rika, trimellitic acid ester compound), polybutene OH (Idemitsu Kosan, polybutene), DOTP (Shin Nippon Rika, tetrahydro) (Di-2-ethylhexyl phthalate)
Example 1 was repeated, except that The results are shown in Table 1. Regarding the viscosity after concentration, polybutene 0H
Only some of the plasticizer was distilled off. Comparative Example 1 Example 1 was repeated except that no plasticizer was used and 10 mL of n-heptane was used as the solvent. The results are shown in Table 1.

Table 1 Hydrosilylation reaction rate [%] Viscosity after concentration Plasticizer species 5 minutes 15 minutes 60 minutes 240 minutes [poise] Example 1 PS-32 39 53 53 87 98 500 2 TOTM 38 60 78 78 97 800 3 polybutene 0H 35 55 82 98 800 4 DOTP 40 60 85 85 98 250 Comparative Example 1 n-heptane 38 58 83 83 97 8000 Example 5 Tetra having an allyl ether group introduced into both ends at a ratio of about 80% and a molecular weight of about 5,000. 10 g of methylene glycol polymer and 6 g of plasticizer DOP (Kyowa Hakko)
Was weighed into a four-necked flask and heated and mixed at about 70 ° C. to obtain a uniform solution.

Next, in a nitrogen atmosphere, 510 mg of methyldimethoxysilane was added, and after mixing, a platinum-vinylsiloxane complex solution (xylene solution: 8.3 × 10 ⁻⁵ mm in terms of Pt) was added.
ol / μL: Pt _n (ViMe ₂ SiOSiMe ₂ Vi)
_m ) was added thereto, and the mixture was heated and mixed at about 70 ° C., and sampled with the passage of time to perform H-NMR / FT-IR
By performing the measurement, the reaction rate of hydrosilylation was calculated from the rate of vinyl group disappearance. The results are shown in Table 2. The viscosities after concentration shown in Table 2 are those obtained after concentration under reduced pressure at 80 ° C for 1 hour and cooling to 30 ° C. Comparative Example 2 Example 5 was repeated except that 10 mL of toluene was used as the solvent without using the plasticizer. The results are shown in Table 2.

Table 2 Hydrosilylation reaction rate [%] Viscosity after concentration Plasticizer species 5 minutes 15 minutes 60 minutes 240 minutes [Poise] Example 5 DOP 30 42 60 88 88 300 Comparative Example 2 Toluene 33 47 67 90 90 Crystallization Table 1 As is clear from the results of Examples 1 to 5 shown in Tables 1 and 2, compatibility with the polymer of the component (A) and conditions such as not inhibiting the hydrosilylation reaction between the component (A) and the component (B). By selecting a plasticizer satisfying the condition (1), the viscosity of the obtained functional group-containing polymer is significantly reduced without lowering the reactivity with the component (B), and the process of paying out and transferring the polymer is It can be seen that not only can it be simplified, but the solvent recovery step can also be omitted.

[0027]

INDUSTRIAL APPLICABILITY The present invention can greatly reduce the viscosity of the obtained functional group-containing polymer without lowering the reactivity, and can simplify the paying-out and transferring steps of the polymer, thereby reducing the solvent recovery step. It is possible to provide a method for producing a functional group-containing polymer which can be omitted.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-4-103606 (JP, A) JP-A-1-170604 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08F 8/00-8/50

Claims (4)

(57) [Claims] 1. (A) It has at least one alkenyl group in one molecule and has an average molecular weight of 500 to 200,0.
And a polymer of (B) the following formula H-[-Si (-R ¹ _b ) (-X _2-b ) -O-]-Si (-R ² _a ) (-X _3-a ). [Wherein, R ¹ and R ² are each an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms or a triorganosiloxy group, May also be different. X is a hydroxyl group or a hydrolyzable group, and when two or more are present, they may be the same or different. a is 0, 1, 2 or 3 and b
Is 0, 1 or 2, and m is 0 or an integer of 1 to 18. ], A petroleum-based process oil, trimellitic acid ester-based compound, tetrahydrophthalic acid diester
-2-A method for producing a functional group-containing polymer, which comprises reacting in the presence of a plasticizer selected from the group consisting of 2-ethylhexyl and dioctyl phthalate. 2. The method according to claim 1, wherein the main chain of the polymer of the component A is composed of saturated hydrocarbon. 3. The method according to claim 1, wherein the repeating unit constituting the main chain of the polymer of the component A is a unit derived from isobutylene. 4. The method according to claim 1, wherein the main chain of the polymer of the component A is hydrogenated polybutadiene or hydrogenated polyisoprene.