JPS6076523A - Novel block copolymer and its production - Google Patents

Abstract

PURPOSE:To produce a specific block copolymer having excellent lubricity and antistaticity, either by the homopolymerization of formaldehyde or by the copolymerization of formaldehyde, etc. with a cyclic ether, in the presence of a specific polymer as a molecular weight regulator. CONSTITUTION:The objective block copolymer having a number-average molecular weight of 10,000-500,000 and composed of a polyacetal and the siloxane- alkylene oxide polymer having the structure of formula is produced either by the homopolymerization of formaldehyde or by the copolymerization of formaldehyde, trioxane or polyoxymethylene with a cyclic ether, in the presence of a siloxane-alkylene oxide polymer of formula (R1 and R2 are H, alkyl or phenyl; X is 0 or methylene; a and b are 1-1,000; n is 2-6) having 1-2 hydroxyl groups, carboxyl groups or amino groups at the chain terminals (e.g. dimethylsiloxane-ethylene oxide).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel block copolymer, and particularly to a novel block copolymer having unprecedentedly excellent lubricating performance and antistatic performance, and a method for producing the same.

Polyacetal is usually obtained by homopolymerizing formaldehyde or copolymerizing formaldehyde, trioxane, and a cyclic ether.

No. 1i935-9435 states that the molecular weight of a formaldehyde polymer is determined by the amounts of trace amounts of water, methanol, and formic acid present in the polymerization system. Further, in US Pat. No. 3,017,389, alcohols, esters, acid anhydrides, amides,
There is a description that formaldehyde is polymerized in the coexistence of a chain transfer agent such as an imide.

Japanese Patent Publication No. 41-21638 discloses the addition of methylal, acetal, formic acid, etc. as a chain transfer agent during the copolymerization reaction of trioxane. Furthermore, JP-A No. 48-29843 describes the copolymerization of trioxane in the presence of polyether.

Furthermore, in Japanese Patent Publication No. 56-42611, the terminal hydroxyl group of a formaldehyde polymer is reacted with triorganohydroxysilane to stabilize the polymer.
Me A Helmet Sparrow 7 h I 1 8 Su Maka Tokuko Showa 35-2194
The publication discloses that formaldehyde is polymerized in the presence of a polymer such as polytetramethylene glycol.

No matter which method is used, it is not possible to simultaneously improve the lubricating performance and antistatic performance of polyacetal.

The present inventors have extensively studied molecular weight regulators to be used during polymerization, and have found that a certain specific polymer functions as a good molecular weight regulator. As a result, we have discovered a new block copolymer that has both extremely excellent lubrication and antistatic properties that have not been seen in conventional polyacetals. Furthermore, this block copolymer is endowed with the high strength and rigidity that characterizes polyacecool. Therefore, the block copolymer of the present invention can be appropriately called a polyacetal having a high degree of performance.

That is, the present invention combines an acetal polymer and a siloxane.
The present invention relates to a novel block copolymer with a high molecular weight, the main component of which is a polymer having a number average molecular weight between 10,000 and 500,000.

Furthermore, the present invention involves homopolymerizing formaldehyde in the presence of a polymer having one or two hydroxyl groups, Cal I xyl groups, or amine groups at the terminals of the siloxane-alkylene oxide polymer, or by homopolymerizing formaldehyde, trioxane, and The present invention relates to a method for producing a novel block copolymer characterized by copolymerizing a compound selected from the group consisting of polyoxymethylene and a cyclic ether.

The block copolymer of the present invention has a friction coefficient of 0.15 to 0.
．． 30 value and surface electrical resistance I x 101O~5X1
It has a value of 0.016Ω, and has unprecedented excellent lubrication performance and antistatic performance.

These excellent performances are based on the block structure of the acetal polymer and siloxane-alkylene oxide polymer of the present invention, and at the same time, this block structure
It is based on a siloxane-alkylene oxide polymer with molecular weight control function. Therefore, it goes without saying that the block copolymer of the present invention has a desired molecular weight.

Demand for polyacetal as an engineering snack has been increasing in recent years, and improvements in the lubricating performance and antistatic performance of polyacetal have great industrial significance.

Next, the block copolymer of the present invention will be specifically explained.

The block copolymer of the present invention is selected from the acetal polymer and the general formula (R+=hydrogen, alkyl group, phenyl group), and each may be the same or different.

R2: selected from hydrogen, an alkyl group, and a phenyl group, each of which may be the same or different.

It is a block copolymer composed of a siloxane-alkylene oxide polymer having a structure represented by

Here, the acetal polymer includes an acetal homopolymer and an acetal copolymer.

Acetal homopolymer is oxymethylene unit +0
It is a polymer consisting of repeating H20+.

Acetal copolymers are oxyalkylene units (formula: selected from hydrogen, alkyl groups, and allyl groups, each of which may be the same or different; m = 2 to 6) in a chain consisting of oxymethylene units. The insertion rate of oxyalkylene units in the polymerized acecool copolymer having a randomly inserted structure is 0.05 to 50 mol, more preferably 0.1 mol per 100 mol of oxymethylene units.
~20 moles.

Examples of oxyalkylene units include oxyethylene units, oxyzolopyrene units, oxytrimethylene units,
There are oxytetraethylene units, oxymethylene units, oxyphenylethylene units, etc.

Among these oxyethylene units, from the viewpoint of improving the physical properties of the graft copolymer, oxyethylene units +
(a horse) 20-1- and oxytetraethylene units ÷ (
OH2)40+ is particularly preferred.

Siloxane, which is a component of the block copolymer of the present invention.
The alkylene oxide polymer is a block copolymer with alkyleneoxy P units of the general formula, and each component is bonded by X ([5iff element or methylene group). Here, a and b are selected from 1 to i, o o o. When a is 0, the sliding performance becomes extremely poor.

Furthermore, when b is 0, the antistatic performance is significantly reduced.

On the other hand, when a is 1.000 or more, the strength and rigidity of the block copolymer with the acetal polymer are greatly reduced. The same applies when b is 1.000 or more.

Here, specific examples of siloxane-alkylene oxide polymers are as follows.

Dimethylsiloxane-ethylene oxide copolymer (a=
501b=150, x=nitrogen)dimethylsiloxane-
Ethylene oxide/propylene oxide copolymer (a=
10. b = 100°
=ao, b=2oo, x=oxygen) diphenylsiloxane-ethylene oxyto copolymer (a=10, b=800
, X = oxygen) methylphenylsiloxane-styrene oxide copolymer (a = 5 + l, = = 30 + X
"methylene group) dimethylsiloxane-ethylene oxide/styrene oxide copolymer (a=250, b=1
5, X = oxygen, ethylene oxide/styrene oxide = 14/1 weight ratio>) The content of the siloxane-alkylene oxide polymer in the block copolymer needs to be in the range of 0.2 to 40% by weight. If the content of siloxane-alkylene oxide polymer is too low, blockco, i?
IJ Mama - Lubrication performance and antistatic performance become poor. On the other hand, if the content is too high, the strength and rigidity of the block copolymer will decrease.

The number average molecular cap of the block copolymer of the present invention is 10.0
It needs to be in the range from 00 to so o, o o o. The lower limit of the number average molecular weight is restricted by the physical properties of the block copolymer, and the upper limit is restricted by the moldability of the block copolymer.

The number average molecular weight of the block copolymer is determined by the following method. In other words, if the number average molecular weight is 100,000 or less, the osmotic pressure method or end group determination method is used, and if the number average molecular weight is 100,000 or more, the weight average molecular weight determined by the light scattering method is used. The number average molecular weight is determined by combining this with the elution curve determined by the gel chromatography method (O, P, A method).

The block copolymer of the present invention is a block copolymer of an acetal polymer and a siloxane-alkylene oxide polymer (D), and is AB or FiA -
It has the structure B-A.

The structure of the block copolymer of the present invention is confirmed by the following method. That is, when a block copolymer is hydrolyzed in an acidic aqueous solution, the portion consisting of repeating oxymethylene units in the acetal polymer turns into formaldehyde, and the portion of oxyalkylene units inserted into the acetal copolymer turns into formaldehyde. , becomes alkylene glycol. Formaldehyde, alkylene glycol,
The siloxane-alkylene oxide polymer contained in the block copolymer is analyzed and quantified using means such as gas chromatography and liquid chromatography. Since the bond with the alkylene oxide is severed, it is decomposed into a cyclic siloxane oligomer, a linear siloxane oligomer, and a hyperpolyalkylene oxide. These compounds are also analyzed and weighed by gas chromatography, liquid chromatography, etc.

Next, a method for producing the block copolymer of the present invention will be described.

The block copolymer of the present invention has a general formula (mountain: selected from hydrogen, alkyl group, and phenyl group), which may be the same or different.

R2: selected from hydrogen, an alkyl group, and a phenyl group, each of which may be the same or different.

1 to 1 to 1.000b: 1 to 1,000n22 to 6) A polymer having one or two hydroxyl groups, carboxyl groups, or amine groups at the end of the siloxane-alkylene oxide polymer having a structure represented by the following formula: It is obtained by homopolymerizing formaldehyde or copolymerizing a cyclic ether with a compound selected from the group consisting of formaldehyde, trioxa/and polyoxymethylene, in the presence of a polymer.

Here, the siloxane-alkylene oxide copolymer is
It functions as a molecular weight regulator during homopolymerization and copolymerization, adjusting the molecular weight of the polymer, and at the same time is injected into the polymer as a block macromer.

The siloxane-alkylene oxide copolymer used as a molecular weight modifier in the present invention must have one or two hydroxyl groups, carboxyl groups, or amino groups at the terminals of the polymer.

When a polymer having one hydroxyl group, carboxyl group, or amine group at the end is used, an A-B type block copolymer is produced, and a polymer having two hydroxyl groups, carboxyl group, or amine group is produced. When used, an ABA type block copolymer is produced.

Here, one hydroxyl group, carboxyl group,
When amino groups are located, these functional groups can be located either on the polysiloxane side or on the polyalkylene oxide side. However, from the viewpoint of strengthening the bond between the acetal polymer and the siloxane-alkylene oxide polymer, it is preferable that one functional group be located on the polyalkylene oxide side.

Specific examples of siloxane-alkylene oxide polymers used as molecular weight modifiers are as follows.

Dimethylsiloxane-ethylene oxide copolymer (a=
50, b=150, X=oxygen, 1 hydroxyl group) dimethylsiloxane-ethylene oxide/propylene oxide copolymer (a=10, b=100 lX=methylene group, ethylene oxide/propylene oxide=l/l<
Weight ratio>, 2 hydroxyl groups) dimethylsiloxane-propylene oxide copolymer (a=10, b=800, X
= oxygen, 2 hydroxyl groups) diphenylsiloxane-ethylene oxide copolymer (a = 10. b = 800 lX = oxygen, force y & 1 xyl group) methylphenylsiloxane-styrene oxide copolymer (a = 5 + 1 ) = = 30 + X = methylene group,
(1 hydroxyl group, 1 amino group) dimethylsiloxane-ethylene oxide/styrene oxide copolymer (11=250.b=15, X-oxygen,
ethylene oxide/styrene oxide = 14/1 weight ratio, one hydroxyl group, one carboxyl group) In addition to these diblock copolymers, (A: selected from hydrogen, alkyl group, phenyl group) Each may be the same or different.

It is also possible to use a siloxane-alkylene oxide triblock copolymer having the structure represented by b': 1 to 1,000 d: 2 to 6) as a molecular weight regulator. Specific examples of this triblock copolymer are as follows.

Dimethylsiloxane-ethylene oxide copolymer (a=
50. b=1501b'=150. X = oxygen, hydroxyl group 2
) Dimethylsiloxane-ethylene oxide/propylene oxide copolymer (a=10, b=100, b'=10
0° is desirable. Moreover, these siloxane-alkylene oxide polymers can be used alone, or two or more kinds can be mixed and subjected to polymerization.

In the homopolymerization of the present invention, sufficiently purified formaldehyde is used, and in the copolymerization, sufficiently purified formaldehyde, trioxane, polyoxymethylene, and cyclic ether are used as starting materials for the acetal polymer.

Here, polyoxymethylene is a homopolymer of formaldehyde or trioxane, and has a number average molecular weight of 1.
0,000 to soo, ooo, preferably 30.00
0 to 150,000.

The first group of cyclic ethers has the general formula (no: selected from hydrogen, alkyl group, and aryl group, each of which may be the same or different. m = 2 to 6)
) There is an alkyleneoxy 1 represented by Examples include ethylene oxide, zolopyrene oxide, butyleneoxy P, epichlorohydrin, styrene oxide, oxetane, 3,3-bis(chloromethyl)oxetane, tetrahydrofuran, and oxenozone. Among these alkylene oxides, ethylene oxide is particularly preferred.

A second group of cyclic ethers includes the general formula % all formals. Among these cyclic formals, ethylene glycol formal, diethylene glycol formal and 1,4-titanium diol formal are particularly preferred.

The cyclic ether is 0.03 to 10 parts by weight of formaldehyde P1 trioxane and 100 parts by weight of polyoxymethylene.
0 parts by weight, more preferably 0.1 to 50 parts by weight are used.

An anionic polymerization catalyst and a cationic polymerization catalyst are used in the homopolymerization and copolymerization of the present invention.

Typical groups of anionic polymerization catalysts include alkali metals such as sodium and potassium, alkali metal complexes such as sodium-naphthalene and potassium-anthracene, alkali metal hydrides such as sodium hydride, and alkaline earths such as calcium hydride. Metal hydride, sodium methoxy P.

Alkali metal alkoxides such as potassium t-cytoxide, alkali metal salts of carzenate such as sodium casilonate and potassium stearate, alkaline earth metal salts of cargenate such as magnesium caproate and calcium stearate, n-f thylamine, diethylamine, Amines such as trioctylamine and pyridine; quaternary ammonium salts such as ammonium stearate, tetrazotylammonium methoxide, and dimethyl distearyl ammonium acetate; phosphonium salts such as tetramethylphosphonium zolobionate and trimethylbenzylphosphonium ethoxy P; Tetravalent organic tin compounds such as tributyltin chloride, diethyltin dilaurate, dizotyltin dimethoxide,
Examples include alkyl metals such as n-butyllithium and ethylmagnesium chloride.

Cationic polymerization catalysts include tin tetrachloride, tin tetrabromide, titanium tetrachloride, aluminum trichloride, zinc cyclide, nonadium trichloride, antimony trifluoride, boron trifluoride, and boron trifluoride diethyl etherate. , so-called Friedel-Crafts type compounds such as boron trifluoride acetic anhydrate, boron trifluoride coordination compounds such as boron trifluoride triethylamine complex, perchlorine, acetyl verchlorate, hydroxy acids #! jChloroacetic acid, p-) A
/ Inorganic acids and organic acids such as efsulfonic acid, salt-free compounds such as triethyloxynium tetrafluorophosphate, triphenylmethyl hexafluorophosphate, allyldiazonium hexafluorophosphate, allyldiazonium tetrafluoroselate, diethyl zinc, Examples include alkyl metals such as triethylaluminum and diethylaluminum chloride.

These anionic polymerization catalysts and cationic polymerization catalysts are used in an amount of 0,000 to 5 parts by weight based on 100 parts by weight of the starting material. Homopolymerization or copolymerization is carried out without a solvent or in an organic medium.

Organic media that can be used in the present invention include n
-Aliphatic hydrocarbons such as pentane, n-hexane, n-hebutane, n-octane, cyclohexane, and cyclopentane, aromatic hydrocarbons such as benzene, toluene, and xylene, methylene chloride, chloroform, and tetracarbons , ethyl chloride, halogenated aliphatic hydrocarbons such as trichloroethylene, and halogenated aromatic hydrocarbons such as chlorobenzene and 0-dichlorobenzene. These organic media may be used alone or in combination of two or more. The siloxane-alkylene oxide polymer, which is a molecular weight regulator, is used after being uniformly dissolved or dispersed in the reaction system. The concentration of the molecular weight modifier in the system can be easily determined experimentally depending on the molecular weight requirements of the desired block copolymer.

The polymerization temperature is usually set between -20 and 230°C,
In the case of no solvent, the temperature is more preferably between 20 and 210°C;
When an organic medium is used, the temperature is more preferably between -10 and 120°C.

There are no particular restrictions on the polymerization time, but it is set between 5 seconds and 300 minutes.

After a predetermined period of time has elapsed, a terminator is added to the reaction system to complete the polymerization. The resulting polymer is stabilized by removing unstable y-ends by hydrolysis or blocking unstable ends by a method such as esterification. Stabilized block copolymers are put into practical use with the addition of stabilizers and the like.

The features of the block copolymer of the present invention and its production method which have been described in detail above are listed below.

(1) The block copolymer has excellent lubrication performance and antistatic performance.

(2) By using a specific siloxane-alkylene oxide polymer, it is possible to obtain a block copolymer with excellent properties and at the same time to control the molecular weight of the polymer as desired.

The measurement items in the following examples are as follows: OMI: 2,2-methylene-bis(4-methyl-(
0.25 parts of 1-tcrt-butylphenol) and 0.50 parts of nylon 6-6 were added and pelletized using a 50 φ extrusion mode. The MI of this pellet is a measure of.

Friction coefficient: The above pellet was formed into a flat plate, and the friction coefficient of this flat plate was measured using a thrust type friction and wear tester under the following conditions.

Matching material: Metal (8450) Load: 10Kg/cn? Linear speed: 12an/sec.

The wear coefficient is an index of lubrication performance.

Surface electrical resistance - The above pellet was molded into a flat plate, and the surface electrical resistance of this flat plate was measured at 20°C and 50% R and H. Surface electrical resistance is an indicator of antistatic performance.

Example 1 (1) Production method of block copolymer Formaldehy P with a purity of 99.9% was mixed at 100% per hour.
(hereinafter, parts indicate parts by weight), 2 og/l of dimethylsiloxane-ethylene oxide copolymer (hereinafter abbreviated as DM8-BO copolymer) having the following structure as a molecular weight regulator, and a polymerization catalyst. as 2.5 x 10-
'ma+,/l dimethyldistearyluane was continuously fed for 3 hours.

DMS-BO copolymer: H3C)! 3 At the same time as formaldehyde gas was supplied, 20 g// of DMS-BO copolymer, 2.5 X 10-' mo+
,/l of toluene containing dimethyl distearyl ammonium acetate was also continuously fed for 3 hours at a rate of 500 parts per hour. Formaldehyde gas was also continuously supplied at a rate of 100 parts per hour for 3 hours, during which time the polymerization temperature was maintained at 60°C. Toluene containing the polymer was continuously extracted in proportion to the amount supplied, and the polymer was separated by initial filtration. After thoroughly washing the polymer with hot toluene, it was vacuum dried at 60°C to obtain 308 parts of a white polymer.

C) Confirmation of structure of block copolymer 5.00 parts of the polymer obtained in (1) was dispersed in 95 parts of 0.3N hydrochloric acid aqueous solution and heated at 98° C. for 3 hours.

Through this heating operation, all of the acetal polymer consisting of oxymethylene chains returned to formaldehyde. Note that the amount of formaldehyde was 4.50 parts. This solution also contains polyethylene glycol (In 1780
) and 0.42 parts of cyclic siloxane and chain siloxane in terms of polydimethylsiloxane.

After acetylating the polymer obtained in (1), terminal group analysis and quantitative analysis using infrared absorption spectroscopy revealed that terminal acetyl group/CH2O chain 75X10'''' mo+
, /Fno+.

obtained the value of From this fact, it became clear that Un of the acetal polymer in the block copolymer (1) was 4.0×10'.

From the above analysis results, it has become clear that the polymer obtained in (1) is a block copolymer of dimethylsiloxane-ethylene oxide polymer and acetal polymer having the following structure.

H3 Hs The content of siloxane-alkylene oxide polymer in this block copolymer is 10.1% by weight.

(3) Measurement of physical properties of block copolymers When a stabilizer was added to a polymer that had been terminally stabilized using acetic anhydride and molded, a very tough molded product could be obtained. The physical properties of this molded article are as follows.

MI 1zo (g/io min) Coefficient of friction 0.22 Surface electrical resistance axlo" (Ω) Thus, this block copolymer has the desired molecular weight and is excellent in lubricating performance and antistatic performance. .

Example 2 (4) Production method of block copolymer Formaldehy r was used at a rate of 100 parts/hr, ethylene oxide was used at a rate of 22 parts/hr, and a1 was used as a molecular weight regulator.
Dimethylsiloxa-1-7 with the following structure in g/z
-1-j upper J + town, t* -φ to t-h / l + Iτ
ts/'t Thl#Oun copolymer) was continuously fed into 500 parts of toluene for 5 hours.

KO-DMS-EO Copolymer H3 Toluene containing the WO-DMS-EO copolymer at the above concentration was also continuously supplied at a rate of 500 parts/hr for 5 hours. In addition, as polymerization catalysts, tetrazotylammonium acetate and boron trifluoride dibutyl etherate were continuously supplied through separate conduits for 5 hours at a rate of 0.03 parts/hr and 0.06 parts/hr, respectively, and polymerization was carried out. The temperature was maintained at 60°C during this time. The polymer was separated from toluene, then washed and dried to obtain 5.20 parts of polymer.

(5) Confirmation of structure of block copolymer The polymer obtained in (4) was hydrolyzed under the same conditions as in Example 1 to obtain a formaldehyde content of 4.24 parts. Furthermore, by quantifying the amount of ethylene glycol in the hydrolysis solution, the insertion rate of oxyethylene units in the acetal polymer was determined to be 1.5.
The results were obtained as follows: mol,/l OOmol, OH20 chain.

In addition, polyethylene glycol (
It contained 0.37 parts of In 1780 ) and 0.39 parts of a siloxane compound in terms of polydimethylsiloxane.

After acetylating the polymer obtained in (4), we analyzed and quantified the terminal acetyl groups and found that the terminal acetyl groups/0
H20 chain = 150 x 10-' mol, /i
A value of no+ was obtained.

This fact shows that U of the acetal polymer of the polymer (4)
It turns out that n is 4.0×104.

From the above analysis results, it became clear that the polymer obtained in (4) had the following structure.

OH3 OH3
+ -10 (0H20#oC) (!H20SH indicates that 10 oxyethylene units are randomly inserted into 670 oxymethylene units.) Also, this block copolymer The content of siloxane-alkylene oxide polymer in xs and a is weight %.

+6) Measurement of physical properties of block copolymer The polymer obtained in (4) has the following physical properties.

MI 10.8 (g/10 min) Coefficient of friction 0.22 Surface electrical resistance I x 10” (Ω) This block copolymer also has the desired molecular weight and is a novel polymer with excellent lubrication and antistatic performance. It is.

Example 3 (7) Production method of block copolymer Polyoxymethylene 5.02 sufficiently dried under reduced pressure
Kg, 420 gs of ethylene glycol formal, 1.26 Kf of diphenylsiloxane-ethylene oxide/zolopyrene oxide copolymer having the following structure, and 50 gs of hexane were charged into a reaction tank as a molecular weight regulator.

During slow charging, after heating the contents of the reaction tank to 70°C, add boron trifluoride (dibutylene tere) 1.27 to the reaction tank.
g was added to start the reaction.

After maintaining the internal temperature of the reaction tank at 70°C for 32 minutes, 130 g
of tributylamine was added to stop the reaction.

After separating the polymer by filtration, it was washed 5 times with a large amount of methanol, and 6
．． 48 Kf of polymer was recovered.

(8) Confirmation of structure of block copolymer The results of hydrolysis of 5.00 parts of the polymer obtained in (7) were obtained.

Amount of formaldehyde: 4.07 parts Also, after acetylating the polymer obtained in (7), the terminal groups were quantified, and the Nln of the acetal polymer of the polymer in (7) was determined.
obtained the results of a, oxio'.

From the above results, it was clear that the polymer obtained in (7) had the following structure.

(Here, X2- + (0HtO ÷ 0H20H20+H) indicates that 1.5 oxyethylene units are randomly inserted into 100 oxymethylene units of too t, s.

) The content of siloxane-alkylene oxide polymer in this block copolymer was 18.7M.

The polymer obtained in (7) has the following physical properties:
24.2 (g/lo min) Friction coefficient o, 26 Surface electrical resistance 5xzo' (Ω) This block copolymer also has a desired molecular weight and is excellent in lubricating performance and antistatic performance.

Example 4 (1()) Production of block copolymer 500 parts of sufficiently purified trioxane, 10 parts of ethylene oxide, and a dimethylsiloxane-ethylene oxide copolymer having the following structure as a molecular weight regulator were placed in a kneader having two Σ-type stirring blades. Charge 121 parts of polymer, 7
Heated to 0°C.

? Then, 0.40 parts of boron trifluoride dibutyl etherate was added to the kneader, and the mixture was pressed for 35 minutes.

After sieving for 35 minutes, 15 parts of tributylamine was added to stop the polymerization. Take out the contents from the kneader.
After thorough washing with hot toluene, 568 parts of polymer were recovered.

(II) Confirmation of structure of block copolymer (The polymer obtained in step 11 was confirmed to have the following structure as a result of 1. hydrolysis and infrared absorption spectrum analysis.

Xs −+ (OH20 momme 0H20H20 OmoH (here Xs−+(OH20p 0H20HxO:!−)−
H indicates that 6 oxyethylene units are inserted into the syndam among 300 nooxymethylene units. ) The content of the siloxane-alkylene oxide polymer in this block copolymer was 19.5% by weight.

(1) Measurement of physical properties of block copolymer (10) The polymer obtained in step 10 has the following physical properties.

MI 218 (g/10 min) Friction coefficient 0.23 Surface electrical resistance I X l o12 (Ω) This block copolymer also has a desired molecular weight and has excellent lubrication and antistatic performance.

Comparative Example 1 (method of Japanese Patent Publication No. 35-2194) (Kon) Polytetramethylene glycol (Ml1
7. 320 parts of a polymer was obtained by carrying out the same procedure as in Example 1, except that ZOO) was used at a concentration of 2o, og/l.

Confirmation of the structure of the polymer When the structure of the polymer obtained in (#) was analyzed using the same method as in Example 1, the presence of the following 23 types of polymers was confirmed.

H
(6) HO-1(-on,), o7toC-0H(t)(埒) Measurement of physical properties of the polymer (The physical property values of the polymer obtained by the method are as follows.

Ml 115 (g/10 min) Coefficient of friction 0.35 Surface electrical resistance 8 x 1016 (Ω) Although it is possible to adjust the molecular weight by using polytetramethylene glycol, the lubricating performance and antistatic performance of this polymer is defective.

In addition, acetal homopolymer I(0+CH2O+-H 310 The physical properties of the molded article obtained are as follows.

Ml 120 (g/10 min) Friction coefficient o, 36 Surface electrical resistance > 1616 (Ω) In addition, the physical property values of the molded product obtained from acetal codelimer Ho-f% aH, oOHz 0H2otH are as follows. .

MI 12B (g/10 min) Friction coefficient 0.36 Surface electrical resistance >1016 (Ω) Examples 5-11 Using starting materials as shown in Table 1 and siloxane-alkylene oxide polymers, blocks shown in Table 1 were prepared. A copolymer was obtained. These block copolymers are all novel polymers and have excellent lubricating performance and antistatic performance. Further, each polymer has a desired molecular weight.

Comparative Examples 2 to 3 (method of Japanese Patent Publication No. 35-2194) No. 1
The block copolymers shown in Table 1 were produced using starting materials and polymers having active hydrogen atoms as shown in the table. When a polymer having mere active hydrogen atoms is used as a molecular weight modifier, it is not possible to simultaneously improve lubricating performance and antistatic performance.

Procedural amendment filed on January 6, 1980 Kazuo Wakasugi, Commissioner of the Patent Office1, Indication of the case 1983 Tokuhoki No. 1831992, Name of the invention Novel block copolymer and method for producing the same 3.1in.

Claims (1)

[Scope of Claims] (1) Acetal polymer and a compound having the general formula (uniform: selected from hydrogen, alkyl group, phenyl group, each of which may be the same or different. R2=hydrogen, alkyl group, phenyl group) X: oxygen, methylene group a: 1-1,000 b = 1-1,000 n: 2-6) A siloxane-alkylene having a structure represented by: A several thousand block copolymer (2) composed of an oxide polymer and an acetal polymer containing oxymethylene units +
The copolymer (3) according to claim 1, which is an acetal homopolymer consisting of repeating OH20+. The acetal polymer has oxyalkylene units (Ro: hydrogen, alkyl group, The copolymer (4) according to claim 1, which is an acetal copolymer having a structure in which m: 2 to 6) is inserted, and each of the phenyl groups may be the same or different. Oxyalkylene unit is oxyethylene units + (OH2) + 0 or oxytetramethylene units 1,000 (OH2) 40+ Claim 1 (5)
Copolymer (6) according to claim 1, wherein the content of the siloxane-alkylene/oxide polymer in the block copolymer is in the range of 0.2 to 40% by weight. R2: Hydrogen, alkyl group, phenyl group, each of which may be the same or different. X: Oxygen, methylene group R: 1- 1,000 b: 1 to 1,000 n: 2 to 6) In the presence of a polymer having one or two hydroxyl groups, carmexyl groups, or amine groups at the terminals of the siloxane-alkylene oxide polymer having the structure represented by A method for producing a novel block copolymer characterized by homopolymerizing formaldehyde or copolymerizing a cyclic ether with a compound selected from the group consisting of formaldehyde, trioxane, and polyoxymethylene (7) Cyclic ether is ethylene oxide, and the manufacturing method (8) according to claim 6, wherein the ether is a compound selected from the group consisting of ethylene glycol formal, diethylene glycol formal, and 1,4-butanediol formal. Manufacturing method according to claim 6