JPS6049002A - Preparation of polyvinylpolysiloxane polymer - Google Patents

Abstract

PURPOSE:To obtain the titled polymer useful as a heat-resistant electrical insulating material, etc. having improved solubility and processing properties, by subjecting a vinylsilane compound to vinyl polymerization to give a prepolymer, subjecting it to polycondensation through dehydration in the presence of a specific jointing agent, silylating the polymer with a terminal stopper. CONSTITUTION:A vinylsilane shown by the formula I (R<1> is hydrocarbon, or fluorine-substituted hydrocarbon; X is hydrolyzable group) or a compound obtained by replacing hydrogen of its vinyl group with fluorine is subjected to vinyl polymerization to give prepolymer having >=1 polymerization degree, which is subjected to polycondensation through dehydration in the presence of a jointing agent such as a compound shown by the formula II, a vinylsilane polymer having <=6 polymerization degree, its hydrolyzate, its hydrolyzed dehydrated condensate, etc., and if necessary, the remaining silanol group is silylated with a terminal stopper such as a compound shown by the formula III or formula IV(Y is bifunctional hydrolyzable group), to give the desired polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing novel polyvinylbolysiloxane polymers.

Currently, there is a strong demand for the emergence of high-performance thermal insulation materials in the field of electronic material production. The following properties are required for the heat-resistant insulating material:

■Have heat resistance of 250"C or more.

■It must be soluble in an appropriate solvent.

■It must be stable after being dissolved in a solvent.

■The ritual membrane can be made thicker.

■The coating film should not crack due to external effects such as heating.

■There should be no pinholes in the paint film.

It has good CD step smoothness and can be used as a step coverage agent for semiconductors.

If a polymer that satisfies these properties is obtained, it can be used as a passivation film for innate materials, %)-disintegration insulation for insulation 1
In addition to opening up applications such as mold and lift-off membranes, it also opens up 12 applications as high-performance insulating materials.

Conventionally, silica, polyimide, etc. have been used as heat-resistant materials in the field of electronic materials, but they are difficult to process.
In terms of things such as 2nd record 11ir@
Dou and iLa are not available ◎ Therefore, Fukakiriron et al. t, 1, polysiloxane purple-based and r
We focused on the fact that siloxane bonds have heat-resistant insulation properties, as seen in silica (SiOi:). Regarding the current usage and moldability of these materials, the former is oily or has a low melting point and is difficult to use as a solid insulating material. The latter is CV IJ (C
bernicalVapourDeposition
) method, etc., and there are many problems with l1iJ thickness, smoothness, etc. Therefore, further attention was paid to lag polymers of siloxane-bonded gold I1.

Ladder polymers are known to be one way to improve the properties, heat properties, etc. of polymers.

However, as a siloxane-bonded gold-free ladder polymer,
Similar to the general formula, a 70-gisane polymer has also been published (tl: J-Kokai No. 56-49540), but the synthesis method is long and there are problems such as the tendency to cause cracks in the coating film, so it is still not in practical use. has not been standardized.

In addition, a ladder polymer containing silane as shown in the general formula has also been synthesized (US Pat. No. 84858570'J#jfl).
There is a problem that the molecular weight is low and the coating film is prone to cracking.

This is because the degree of polymerization of polyvinylsilane is generally not very high, and as shown in previous reports, there is a difference between 2 and 3 using the KM association method.
It is thought that one of the reasons is that the value is less than 0.

The purpose of the present invention is to overcome all the drawbacks of these dielectric ladder polymers and to develop a new polyvinylbolysilogysan polymer which exhibits the above-mentioned properties.

7I-For clarity, the general formula CH2=(JI SiR'Xz
(Here, R1 is a carbide 7J (an elementary group or a Fkk-substituted hydrocarbon; Vinyl silane or a compound in which Ff hydrogen is directly attached to the vinyl group with fluorine (hereinafter collectively referred to as "vinyl silane") is subjected to vinyl polymerization, and the resulting vinyl polymer is treated with an acid or In the method for producing a polyvinylbolysiloxane polymer with a high degree of polymerization, which includes hydrolysis and dehydration in the presence of a base, the vinyl polymer has a degree of polymerization of 7 or more (hereinafter referred to as "prepolymer"). ).
The hydrolyzed dehydrated rice 1f product (hereinafter referred to as "prepolymer etc.") may be the same or different. ), a vinyl polymer of the vinylsilane having a polymerization degree of 6 or more and 1ζ and a polymerization degree lower than 1ji of the prepolymer; Dehydration condensation polymerization is carried out in the presence of a jointing agent consisting of
(Residual silanol group according to rc, general formula R': +Si
X (Here, R1 and X represent the same taste as above, and R1 may be the same polarity or different polarities in the same molecule.), or the general formula R'3Si -Y -8i
R'3 (where Y is a divalent hydrolyzable group p, R
1 represents the same meaning as above, and may be the same type or different types within the same molecule. ) to be silylated with a terminal capping agent! g) A method for producing a self-polymerized polyvinylborisyrogysanne polymer.

As mentioned above, the Mff tf self-grease polymer has a low degree of polymerization, and even if it is hydrolyzed and subjected to intramolecular dehydration condensation to form a coating film from C, it is likely to crack. The present invention uses such a rag-polymer (presumed to be),
rff + distribution j'L'2 SiX2 or the above-mentioned relatively low degree of polymerization polyvinylsilane or their hydrolysis or t, 1 hydrolysis angle 'N/wastewater fh combination as a jointing agent, (hydrolysis) dehydration This is to obtain a combination of high-density parts connected by a net stand. In this case, the higher the degree of polymerization of the prepolymer, the better the heat resistance of the final sieved polymer. Therefore, it is appropriate that the degree of polymerization is at least it'y. On the other hand, since the joint agent increases the speed of the joint reaction (polymerization reaction), it is better to have a smaller molecular weight. Therefore, the degree of polymerization of the relatively low molecular weight polyvinylsilane, its hydrolyzed product, or its hydrolyzed and dehydrated condensate (hereinafter referred to as "low molecular weight polyvinylsilane") used as the jointing agent is also preferably low, and is 6 or less. , 2 or more is appropriate.

Regarding JFJ's ratio of warping of prepolymer, etc. and joint R mountain, (c), preferably 0.8 mol or more of joint agent per 1 mol of prepolymer.
The amount is preferably 1 mole or more, preferably 1 mole or more. The upper limit of l'3'J LC for the joint agent is preferably 20 mol or less, preferably 10 mol or less, and preferably 5 mol or less, per 1 mol of the prepolymer. However, hydrolysis with R"28!
,) is preferably 3 mol or more per mol of prepolymer, whether used alone or in combination with low-molecular polyvinylsilane.

〈 is suitably 2 moles or less.

The high polymerization degree polymer obtained in this way is soluble in a suitable solvent, so it can be easily formed into a coating film, the solution is stable, and the coating film can be thickened. The resulting coating film is resistant to cracks, has no pinholes, has a step height of 19 mm, and has high heat resistance on one side.

A.-The polymer produced according to the invention has a 141 medium value of 50 or more, and a l:1100 or more value.

In the vinyl silane used in the present invention, a part or all of the R1rJ hydrocarbon group or its aqueous system is completely fluorinated, but preferably the carbon atom -f[10° or less]
An alkyl group or a Vj-aryl group, more preferably an anol group having 1 to 4 carbon atoms, or an aryl group having 6 to 9 carbon atoms.

Is it a XQL hydrolyzable group?
-0R2, -()C(H<2, -SR', -'NR
``2, -N1-I R', OS 03 R2 can be mentioned. More preferably &:tL Soki Jk (1 to 4 alkyl groups or aryl groups having 6 to 9 carbon atoms).

This vinyl polymerization of vinyl silane can be carried out using, for example, hydrocarbon threads,
Preferably, alkyl lithium, alkyl aluminum (R3At) in an aliphatic solvent.

R2AtC7: where R stands for Argyl Foundation. ) or a radical polymerization catalyst such as benzoyl peroxide or azobisin butyronitrile. For example, when using methylvinylbis(dimethylamino)silane as a monomer, anionic polymerization can be performed using the organometallic 1l-1; When chlorosilane or methylvinyldichlorosilane is used, radical polymerization can be carried out using the above-mentioned radical polymerization catalyst. The reaction humidity is -10 to 90°C, preferably -5 to 50°C in the case of preself-anionic polymerization, and preferably 50 to 200°C, <70°C in the case of radical polymerization.
~150"CVr:, each can be adopted.

There are already many documents regarding this vinyl polymerization method itself, and the known methods can be applied, and the present invention is not particularly limited thereto.

The upper limit of the degree of polymerization in this vinyl polymerization is at most 20, and it is the inner shaft that achieves a degree of polymerization higher than this.

Next, this vinyl polymer (hereinafter sometimes referred to as prepolymer) is hydrolyzed and subjected to dehydration condensation. Hydrolysis of C is carried out at -5 to 60°C, preferably from 20 to 60°C, using a base or a base as a catalyst, in the presence of water or alcohol for hydrolysis.
The dehydration condensation can be carried out at 50"C. The concentration of the water or t-alcohol can be suitably used in an equimolar to 3 molar degree relative to the 5i-X. The dehydration condensation can be carried out using an acid or a base as a catalyst. It can be carried out in the presence of -5 to 100°C, preferably 20 to 7°C.The above hydrolysis and dehydration condensation e and 1 can also be carried out in a single step reaction.In this case, Q': 6 Self-dehydration condensation reaction It is best to perform this under the same temperature conditions. These additions A
<Decomposition and denomination 1 < Condensation 1
Examples include inorganic acids such as acetic acid, organic acids such as para-toluene sulfone M, and cation exchange resins (especially strongly acidic ones). Examples of the base include hydroxides and carbonates of alkali metals or alkaline earth metals. It has this hydrolysis dehydration line -〇H group. The typical structure of the polymer at this stage is estimated to be as follows.

However, depending on the reaction conditions, silanol residues other than those at both ends may be present.

The joint agent is a silicon compound having two hydrolyzable groups bonded to a silicon atom, or a hydrolysis thereof;
Specifically, it is a compound represented by the general formula R1□5iX2 or a hydrolyzed product thereof, a vinyl polymer having a relatively low degree of polymerization of the vinyl silane, a hydrolyzed product thereof, or a hydrolyzed dehydrated condensate thereof. This joint agent ended up being 5i
It becomes a form with two -OH groups, and a dehydrated crude alloy is formed between the remaining 5i-OH groups of the hydrolyzed and dehydrated condensate of the prepolymer, and a polymer is formed.

R′J
- The hydrolysis of the prepolymer described above or the dehydration of the hydrolysis can be carried out under the same conditions as the 1t6 combination, or they can be carried out separately or simultaneously by mixing G'1. Mix and add the same +1. 'l, as mentioned above, along with the hydrolysis of the polyvinyl run itself > y + dehydration condensation (l (=
- Dehydration of polymers such as salt with jointing agents,
Accommodations will be created.

Ai The above prepolymer or its addition/1 (decomposition/dehydration condensate and the above join)/Jill reaction 1. In the presence of a family or a base in a common solvent, 15~1 (10-C
Preferably 17 (&, done at 1.20-70”C) U this (
A polymer i is formed from this. At this time, the solvent is used to hydrolyze the prepolymer or complete the intramolecular dehydration network alloy of the partially dehydrated condensate thereof to prevent crosslinking reactions, so that the preparation time is 40% based on the final polymer. % or less It is preferable to use the entire amount that will result in a preferable depth of 20% or less. As the solvent, aromatic hydrocarbons such as benzene, toluene, and xylene can be used.

Next, these mixtures are aged in order to proceed with the condensation polymerization of the low molecular weight MSi compounds that did not/reacted in the polymerization reaction and the dehydration condensation between the residual ranol groups in the polymer. It is better. This aging should be done as much as possible: Xi
! j 50-150℃ in water bath state, preferably 70-1
30° ('H-6 is best, in this case reaction
[0.5 to 101Brlfi] can be preferably set to 1 to 5 hours.

At the time of this polymerization, 2 fik or more having different degrees of homopolymerization may be mixed and used in Δ as the prepolymer or the like. As a result, it is possible to widen the molecular weight distribution of the high molecular weight polymer produced in (4) to the maximum extent possible, thereby making it possible to make the coating film even less prone to cracking. A similar effect can be obtained when all of the above-mentioned low molecular weight prepolymers are used in the joint agent.

It is well known that solutions of polysiloxane-based polymers have the problem of gelation during storage due to the amount and nature of residual hydroxyl groups present at both ends and occasionally in the middle of the siloxane chains of the polymer. It's r+
As an end stopper, the general formula R'3SiX
Alternatively, the compound represented by R'3 S + Y S iR's or the hydrolyzed IFt'r form of It is preferable to silylate residual hydroxyl groups to control the residual Lt.

As i1'HpiY, the general formula R'N< (where R
3 is hydrogen or (J, hydrocarbon water having 1 to 4 carbon atoms, (1; or (・
1 represents an acyl group. ), -〇-.

The silylation can be suitably carried out at 20-100'C and no particular catalyst is required.

The molar ratio of the residual hydroxyl groups to Si in the polymer is 0 to 0.1, preferably l-1o, ooi to 0.02.
It is better to

The polymer according to the present invention is easily soluble in aromatic hydrocarbons such as benzene and toluene.

Next, 5i0 according to the present invention and the conventional method C V I) method
Table 1 shows a comparison between the coating film No. 2 (formation method) and the coating film (formation method) of condensed polyimide (PIQ).

Table 1 Example 1 (]) Vinyl ■ Association: L 1 molten Boom / 8 methyl vinyl bis (dimethylamino) silane 54y and n-hexane 90d'f: put into a flask, atom gas vII - 12 mmoL of n-butyllithium catalyst was added to the n-hexane bath solution at room temperature, stirred, and placed on an FK stand. After carrying out the entire I-combination reaction at room temperature for 3 hours, the mixture was treated with methanol to precipitate the polymer. This polymer was repeatedly washed with methanol and filtered 8 to 4 times, and then dried in vacuum. The degree of polymerization was 9.5 from the 1tll constant determined by the freezing point depression method using 10.3 g of the obtained polymer F1, and 'fc
.

(2) Polysiloxane formation reaction (ladder reaction) and polymerization reaction: 500 m purged with nitrogen/200 m in the 8th flask
1 of toluene and 10 g of the polymer obtained in (1) were added, and 15.5+* of glacial acetic acid was added under stirring in nitrogen atmosphere γ'f (f).
t was added dropwise and allowed to react at room temperature. After reacting for 1 hour, dimethyl diacetoxysilane (1511) was added, then water was added dropwise at 1.1 rxt, and the reaction was carried out under stirring for 30 minutes in the room width to form siloxane bonds. Ether was added to the resulting polymer solution. The organic layer was separated and dried over potassium carbonate overnight.After the potassium carbonate was separated in the furnace, it was heated in a hot water bath to distill off the ether. The remaining liquid was heated to 75°C to 85°C.
After heat treatment at C for 1 hour, toluene was distilled off under reduced pressure and the solution was condensed.

A portion of the liquid concentrated to about 10% polymer solution was collected and subjected to infrared absorption spectrum analysis, quantitative analysis of 810H, and molecular W aaj determination.

The weight average molecular weight of the polymer obtained in A31 and 11 was determined by GPC to be 2.5×10', indicating a degree of polymerization several ten times that of the prepolymer obtained in (1). As a result of the infrared absorption spectrum 1j constant, 34500ff-' contains silanol (
Absorption of St-OH) was observed. This flash of hydroxyl, i: is based on the method of G, E, KEI, L'UM et al. Anat,
Chern.

39 1628 (1967) method analysis result Off
/ Si molar ratio was 0.17. From the above results and bath M properties with respect to toluene, it was determined that the obtained polymer had a full ladder structure of 41-7.

This Polymer M solution was spun onto a silicon ribbon wafer, placed in a room, and dried in the sun for 2 days.
Cracks even in the thickness of ll'',! JG was not born. When this solution was left at room temperature for one month, gel formation was observed.

Large Example 2 In exactly the same manner as in Example 1, synthesis of a prepolymer, polysiloxane formation/polymerization reaction, drying using potassium carbonate, and pouring of a polymer bath onto 10% potato were carried out four times. Then this polymer solution (toluene bath solution) hehexamethyldisilazane ((CII,) asiNH8i(CH3)3;
Hereinafter, it will be abbreviated as HIVI L)S. ) 11 total addition 9
The reaction was allowed to take place at 0°C for 1 hour.

As for the residual hydroxyl groups in the obtained polymer, almost no infrared absorption spectrum of 5iOH < 8450 cm was observed, and from the results of quantitative analysis (the same method as in Mitsuyama Shiri 1), OH/St The molar ratio was 0.001 or less.

Disaster Turtle 113 (1) Vinyl lJf combination: 1 history of n-butyllithium catalyst J, i: Total 11ti1
2 4:tl changed to mot and 25111moi
The combination of i was carried out at all times except for the amount of catalyst. Samuraed/C Polymer's LIL
The sum 1i was 10.5 feet and 4.7 feet, respectively.

(2) Polysiloxane formation/polymerization reaction: Using 2.8y of the polymer with a degree of polymerization of 10.5 synthesized in (1) and 8.7 g of the polymer with a degree of polymerization of 4.7, 18 ul of glacial acetic acid was added to Example 1. It was added dropwise in the same manner as above to stir a reaction. After reaction for 1 hour, 1.8 tIIt of water was added dropwise to carry out hydrolytic condensation at room temperature for 30 minutes. The obtained product solution was divided into four parts as in Example 1 by water washing and ether extraction;
It was X104. The polymer solution was condensed at 200+x/l, and this Il was divided into two parts, 1\ of which was added to one, and 85 ml of 14MD was added to the other, and the reaction was carried out under reflux for 5 hours at 130-140''cT. The i.d. liquid sample was reduced to an approximately 10% solution by condensing it under reduced pressure in an 80" cup.

The polymer before adding fl M D S clearly shows silanol absorption (34501v) from the infrared absorption spectrum.
+”) was observed, and the results of t fc and quantitative analysis were also OH/
Yuko's solution, which had an SI molar ratio of O.12, was stored at room temperature and gelatinization was observed when the SI molar ratio was approximately 1.5.

On the other hand, it was found from the infrared absorption spectrum that almost all residual hydroxyl groups in the polymer added with HMDS disappeared. Furthermore, although this melt was kept at room temperature for 4 months, no gelation occurred.
, Il・′) could not be done.

Comparative example (1) Vinyl JIJ-combination: It was carried out in the same manner as in Example 1.

(2) Formation of polysilgysanate (ladder formation) 2 was carried out in the same manner as in Example 1 without adding dimethyldiacetoxysilane. 't: 1r-):Ij The average sufficiency of the polymer was determined to be 10 by the freezing point sieving method.

605% polymer i trough solution was left at room temperature for 1θ days 1,12
Gelation was observed in the silicone wafer, and there was a slight change in the silicone weight. / Dry and (i)'k liM's kt? <The occurrence was reported on i58.

Example 4 (1) Vinyl 41: Methylvinyl di(n-prohogincidine (bp,
6 (1'c/10, j?ff11g) 11.
tJ I was put into a flask with a room temperature of 100 ml, and 0.04 d of azobisisobutyronitrile was added as a radical polymerization initiator, and after replacing with nitrogen gas again, the contents were After 2 hours of polymerization reaction in a 150°C bath, the whole body dried up (jAl became a liquid,
Polymerization was observed, but no color change occurred. Polymerization was stopped after 6 hours, and unreacted monomers were removed from the prepolymer thus obtained by vacuum distillation.
After distillation, 9.5 f (yield: 86%) of polymer was obtained.

(Si) Polysiloxane formation/polymerization reaction: Add 150 grams of toluene and 0.5y of dimethyl di(n~propoxy)silane to 9.0 g of the polymer obtained in (1), and melt and sew. 3 (Transfer 10 ml == 2 flasks, add 100 g 1 water containing 1 tnl gold to it, and then boil at 50'C for 2 hours with stirring)
4 Reaction'', and perform the condensation reaction (t).

Rinse the reaction solution with water and dry thoroughly.

To this toluene solution was added 1.6 ml of hegisamenaldisilazane and reacted for 1 hour with heating at θ.
The resulting polymer bath was concentrated by distilling off 1.luene until it reached 100 trttIIC.

From the infrared absorption spectrum of this solution, the presence of 5iOH groups e
I didn't recognize it. As a result of analysis, the molecular structure of poly 7- in solution 4 was found to be 4. ．． 8 X 1 (1', speed V←112
．． It was a 6' version.

Actual sister example 5 Methyl vinyl di(11-propoxy) silane Radical polymerization was carried out in the same manner as in Example 4 except that methyl vinyl di(11-propoxy) silane was used, and unreacted mono 7- was distilled off. After 7ζ, the analysis showed that the polymer yield was 1!
Calligraphy: J' 8.9 y dewo)tsu/me 0 this polymer 8
g and dimethyl diacetate 4 disilane 0.2y 15
1.04 ml of water was added dropwise to 0 m/' of benzene in a flask of f&K4 L 800 g under stirring at 25°C to stir a reaction. Repeat the water removal ffA-1 separation with the addition of needles for 3 times. 1. Organic, 1t4 is soaked in well water charcoal and cicada potash, dried 2/(. Desiccant stone 11 ~ ether is distilled off. Shitaq:J
t) 0.2 tnl of hexamethyldisilazane was added and reacted for 70''C-C for 2 hours. Part of the benzene was removed from the box, and the excess was reduced to 714 r/z in about 80 liters. two.

The resulting polymer solution had a concentration of 10%, and analysis of the polymer revealed that the molecules were f11'g, 5xlo'.

elm) Il! I 1) 14 5 (]) VinyljjL: Vinyl 7(chill bis(cyenalamino)silane 8
tl, 4 y, n-heginane 120mt and 5L ('no mouse, self 1' + super medium n-) nal lithium Wr r
& (15%) in 10 ml k (d5 yl'j
Except for (-J: Husband) il '5U 1 (1) and D
'J4>fit'=Z f・i,・ite 1~, starting combination j and 9,7 polymer (A) total 21.6? ,;su7
, -8-hinyl methyl his(diethylhumino)silane T6.21. n-hekitoon 120 al jy'
YoOn-bunal lithium iu ji'A 20 yl'
? r, 1-1-River, soil, and place j1; ni operation Z small nail rest r = 5.2・1zarimah (1 momme)'< 40.
IQ, lfk.

(2) Holin 11 Kirin formation/611 min 1′ conversion reaction: a
−, =; ;EIiJ(('Pc! h, fc le
Stop LJ 7 Hun, -'L'C,, t 00 benzene; / and (+) can be removed /, - Polymer (A)
byohi (B)? (i so that 5.1N and 18.Oj7
86 wt of ice vinegar was reacted at 25°C under stirring. After reacting for 30 minutes, dimethyl diacetoxysilane was added and mixed. Then, 2.75πl of water was subjected to a sub-reaction at 30°C while stirring with a filter. Add 300 wl of Tρ ether, which was allowed to react for 50 minutes. This td solution was transferred to a separating funnel, and the steps of washing with water and washing with water were repeated three times, and then the organic layer was collected and dried.

(3) Feminization reaction: Dry the syneresis layer in a hot water bath, distill off the ether, and then distill off part of the benzene until the total volume of syneresis becomes about 300 ml (Harimoto Ii). To this bath solution, 3 ties of hegisamethyl disilazane gold [I] were soaked for 1 hour under a hard flow, and then the pentene purple was distilled off.
．． )lt.

(・1) Polymer 'IyJ1'j2: Analyze this stone t1 father and as a result, limit the polymer. 1, '5.6'
i'o, polymer (average molecular weight (・shi12゜8X10
'Demetsu/(2, lT G A ('l'hermat)
W% k fIJ: start (rjr Ireni l:J,
1 (1' method thermal reduction point was 480°C, indicating good heat resistance. This poly 7-R) liquid ], 000 rpr
Coat it on a silicon wafer with a spinner of 170
When treated with TLFJ8 for 80 minutes at °C, the result was 1.2 p m.
A uniform core and crotch with no cracks was obtained. The electrical properties of this coating film are 8.5 and 8.5. Insulation control 250v/
It was μ772.

Actual A'H Example 7 A silicon wafer was coated with a 15% cure solution of the polyvinylphorysilogysan polymer that was used in Example 11 and Comparative Example 1.3.
Apply spin coating to 1 port 10o.

rJ)m) State of membrane after heat treatment at 150°C for 30 minutes. The result is like the next cloth 2 j5
One.

Table 2 2

Claims (9)

[Claims] (1) General formula CH2=CHSiR"X2 (where R1
X is a hydrocarbon group or a fluorine-substituted hydrocarbon group; ) or a compound in which hydrogen in the vinyl group is replaced with fluorine (hereinafter these are collectively referred to as "vinylsilane") is vinyl polymerized,
In the method for producing a polyvinylbolysiloxane polymer having a high degree of polymerization, which includes hydrolysis dehydration condensation in the presence of a base, the vinyl polymer is 7 or more (hereinafter referred to as "prepolymer") or its hydrolyzed and dehydrated condensate (hereinafter referred to as "prepolymer") f
:, general formula Rm5iX2 (here, R' and 6
Hereinafter, a joint agent consisting of at least one member selected from a vinyl polymer of pre-Nt vinylsilane having a degree of polymerization lower than that of the prepolymer, and their hydrolyzed and dehydrated polymers will be described below. In the presence of
Dehydration condensation polymerization is performed, and if necessary, residual silanol groups are converted into a compound of the general formula R45iX (herein, R1 and X represent the same meanings as above, and R1 may be of the same type or different types within the same molecule). , or general formula R35i-Y 5iR
4 (Here, Y is a divalent hydrolyzable group, R1 represents the same meaning as above, and may be the same type or different types within the same molecule, etc.) A method for producing the above-mentioned highly polymerized polyvinylborisiloxambo IJ-v-, which comprises silylating the polyvinylbolysiloxambo IJ-v- with an agent. (2) The method according to item (1), wherein R1 is a hydrocarbon group having 1 to 10 carbon atoms or a hydrocarbon group having a single fluorine substitution. (3) The % symbol indicates that R1 is an aliphatic hydrocarbon group having 1 to 4 carbon atoms, an aromatic hydrocarbon group having 6 to 9 carbon atoms, or a group in which hydrogen thereof is substituted with fluorine. The method described in (1). (4) The above X is -NR2□, -0R2, -81e2,
-00OR2 or 10 S 03 R2 (R here
7. 2 represents a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 4 carbon atoms. ), or C1, Br, or ■. (5) The method according to any one of items (1) to (4), wherein the vinyl polymerization is carried out using an anionic polymerization catalyst or a radical polymerization catalyst. (6) In the reaction between the prepolymer, etc. and the jointing agent, 0.8 of the jointing agent per mole of the prepolymer, etc.
The method described in any one of paragraphs (1) to (5), characterized in that a total of 20 moles of the compound is present. (7) -Y- is represented by the general formula R'N'< (where R3
is hydrogen, a hydrocarbon group having 1 to 4 carbon atoms, or an acyl group
) or -〇-.
) to (0), the method listed in Isuha, Kani i1. (8) By silylation with the terminal capping agent, the amount of residual water groups in 11iJ is set to 0 to 0.1 in molar ratio with respect to 81 atoms in the polymer. 1) The method of listing 11 items in any of the sections (7) and (7) above. (9) The remaining hydroxyl group is brought to a molar ratio of 0.001 to 0.02 with respect to the Sl atoms in the polymer by silylation using pre-terminated riil.
The method described in any one of paragraphs 1) to (7).