JPS59172512A - New acetal block copolymer and its production - Google Patents

Abstract

PURPOSE:The titled copolymer excellent in impact resistance and fatigue resistance, composed of a polymer of a specified number-average MW and an elastomer and prepared by inserting blocks of an elastomer of a specified secondary transition temperature into the main chain of a linear polymer. CONSTITUTION:An acetal block copolymer having a structure in which blocks of an elastomer of a secondary transition temperature of -120-+40 deg.C are inserted into the main chain of a linear polymer and being a triblock copolymer of an A-B-A type wherein A is an acetal polymer of a number-average MW of 10,000-500,000 and B is the elastomer. Said A consists of a homopolymer comprising repeating oxymethylene units of formula I or a copolymer in which the oxyalkylene units of formula II (wherein R0 is H, alkyl or aryl and m is 2-6) are inserted randomly into a chain comprising the oxymethylene units. It is possible to impart extremely excellent impact resistance and fatigue resistance and improved toughness without detriment to high strength and rigidity.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel acetal block copolymer, and particularly to a novel acetal block copolymer having unprecedentedly excellent impact resistance and fatigue resistance, and a method for producing the same.

Polyacetal is usually obtained by superposing formaldehyde r1 trioxane alone or by copolymerizing formaldehyde, trioxane, and a cyclic ether. Japanese Patent Publication No. 35-9435 states that the molecular weight of a formaldehyde polymer is determined by the amounts of trace amounts of water, methanol, and acid present in the polymerization system. Further, in US Pat. No. 3,017,389, there is a description that formaldehyde is polymerized in the coexistence of a chain transfer agent such as an alcohol, ester, acid anhydride, or imide.

Furthermore, Japanese Patent Publication No. 35-2194 discloses that formaldehyde is polymerized in the presence of polymers such as polytetramethylene glycol, vinyl acetate copolymer, and methyl methacrylate/vinyloxymethylmethylamine copolymer. ing.

The polyoxymethylene block copolymer produced using this method has slightly improved toughness, but has a significant decrease in strength. In other words, this copolymer has too much flexibility, resulting in a significant decrease in strength and rigidity. This fact becomes clear in all comparative examples.

Acetal polymers are useful as engineering plastics because they have well-balanced physical properties. Attempts to improve toughness such as elongation and impact value even at the expense of strength and rigidity, as in the case of the copolymer of the present invention, cannot necessarily be said to be an advantageous direction.

As a result of extensive studies on molecular weight regulators to be used during polymerization, the present inventors discovered that a specific nidistomer consisting of
It has been found that it functions as a good molecular weight regulator. As a result, we have discovered a new acetal clock copolymer that has both extremely excellent impact resistance and fatigue resistance, which have not been found in conventional acetal polymers. Moreover, this block copolymer has improved toughness while maintaining high strength and rigidity.

Therefore, the block copolymers of the present invention can more than be called highly balanced polymers.

That is, in the present invention, in the main chain of the linear polymer, -120 to +4θ
intercalated with a nidistomer having a second-order transition temperature of °C,
The present invention relates to a novel high molecular weight acetal block copolymer whose main component is a polymer having a number average molecular weight between 10,000 and 500,000. The present invention is refreshingly
In the presence of a di-stomer having two functional groups selected from the group consisting of a hydroxyl group, a caroxyl group, and an amide group at the end of the polymer, formaldehyde is polymerized or formaldehyde P and a cyclic ether are combined. The present invention relates to a novel method for producing an acetal copolymer characterized by copolymerization or reaction of polyoxymethylene with a cyclic ether.

The acetal block copolymer of the present invention has an Izod impact value of 15 to 105 to Crn/CMI, and has unprecedented impact resistance. Furthermore, the copolymer of the present invention also has vibration fatigue resistance at the same level as the acetal homopolymer.

These excellent performances are due to the block structure of the polyacetal and elastomer of the polymer of the present invention, and at the same time, this block structure is based on a di-distomer having a molecular weight control function. Therefore, it goes without saying that the polymer of the present invention should have a desired molecular weight.

Demand for acetal polymers as engineering plastics has increased more and more in recent years, and improvements in toughness such as impact resistance and fatigue resistance of acetal polymers have great industrial significance.

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

The acetal block copolymer of the present invention is a polymer in which an elastomer having a secondary transition temperature of -120 to +40°C is inserted into the main chain of a linear polymer. It is an ABA type triblock copolymer with 1-(B).

Here, the acetal polymer includes acetal homopoly,
7- and acetal copolymers.

Acetal homopolymer is monooxymethylene 1-4
It is a polymer consisting of repeating -CH, O÷.

Acetal copolymers are oxyalkylene units (Ro: 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. It is a polymer with a randomly intercalated structure.

The insertion rate of oxyalkylene/unit in the acetal copolymer is 0605 per 10 mole of oxymethylene unit.
-50 mol, more preferably 0.1-20 mol.

Examples of oxyalkylene/units include oxyethylene units, oxyzolopyrene units, oxytrimethylene units,
There are oxyctitramethylene units, oxyethylene units, oxyphenylethylene units, etc.

Among these oxyethylene units, from the viewpoint of improving the physical properties of the acetal block copolymer, oxyethylene units +(OH2)20+ and ox7tetodiethylene units +(OH2)40+ are particularly preferred.

The nidistomer to be inserted into the main chain of the acetal block copolymer of the present invention has a second-order transition temperature (glass transition temperature, Tg) of -120 to +40°C.

The term "nidistomer" here refers to a thermoplastic polymer, which is a copolymer of an amorphous segment with a low secondary transition temperature (soft segment) and a segment that creates a thermoreversible cross-linked/bonded structure (hard segment). be.

A first example of the elastomer constituting a component of the block copolymer of the present invention is a styrene-based elastomer with polystyrene as a hard segment. Soft segments to be combined with polystyrene include diene systems such as polycitadiene and polyisoprene, and hydrogenated diene systems such as hydrogenated polycitadiene and hydrogenated polyisoprene. Among these styrene elastomers, polystyrene-polyzotadiene block copolymers and polystyrene-hydrogenated polysitadiene block copolymers are preferred.

A second example of the elastomer is an ester-based elastomer in which the hard segment is made of polyester such as polyethylene terephthalate, polybutylene terephthalate, modified polyethylene terephthalate, or polyethylene-butylene terephthalate. Soft segments to be combined with polyesters include polyethers such as polypropylene glycol, polytetramethylene gelyl, and the like. Among these ester-based distomers, polyzotylene terephthalate-polytetramethylene glycol block copolymer and polyethylene-butylene terephthalate-polytetramethylene glycol block copolymer are particularly preferred.

A third example of the elastomer is an amide-based elastomer, in which the hard segment is made of polyamide such as nylon-6, nylon 6-6, or nylon 6-1θ. Soft segments to be combined with polyamide include:
Examples include polyethers such as polyzolopylene glycol and polytetramethylene glycol, and polyesters such as polyethylene adipate and polyethylene adipate. Among these amide elastomers, nylon-6-polyzolopylene glycol copolymer, nylon-
6-Boritetramethylene glycol brosoccopoly'7
- is preferred.

A fourth example of the entomer is a urethane-based nidistomer, which is made into a urethane t-hard segment.

Here, urethane is diincyanate such as 4,4'-diphenylmethane diisocyanate), 4,4'-dicyclohexylmethane diisocyanate, and ethylene glycol.
It can be obtained by reacting with a glycol such as tetramethylene glycol.

Soft segments to be combined with the urethane include polyester diols such as polyethylene adipate and polyethylene adipate, and 15-riether diols such as polypropylene glycol and polytetramethylene glycol.

Among these urethane-based nidistomers, 4.4-
Polyurethanes synthesized from diphenylmethane diisocyanate, tetramethylene glycol and polytetramethylene glycol are preferred.

The content of the nidistomer component in the linear polymer is 0.5 to 50
It is necessary that the amount be within the range of % by weight. If the content of the elastomer component is too low, no improvement in the toughness of the polymer will be observed; Engineering and rigidity. Decrease Ka=-vbi, b.

The structural formula of the acetal block co-11 combination of the present invention is as follows.

R10+0H20)a' X-(-01-120+H
R1(t)R10+0H20suX→cHzo'j701
'J (5) 1 (X: elastomer component, R1: hydrogen, alkyl group, allyl group, each may be the same or different. a, a', b, b' are (This is a positive number representing a chain, indicating that b oxyalkylene units are inserted into the n unit, and does not specify the distribution of oxyalkylene units in the polymer.) In the structural formula shown, when R1 is hydrogen, (t)
The acetal block copolymers represented by , (2) , (5) and (6) have a hydroxyl group at the end and are unstable. Among these, (1) and (5), which have an acetal homopolymer at both ends, can be put into practical use after converting the terminal hydroxyl group into a stable group using known methods such as esterification, etherification, and urethanization. Served.

Also, (2) and (2) have acetal copolymers at both ends.
6) can be processed by co-workers with (1) and (5), or can be used for refreshing purposes by removing the terminal part of the foot by hydrolysis.

The structure of the acetal block copolymer of the present invention is confirmed by the following method. That is, when an acetal block copolymer is hydrolyzed in an acidic aqueous solution, the repeating portion of the oxymethylene unit becomes formaldehyde,
The portion of the oxyalkylene unit inserted into the acetal copolymer becomes an alkylene glycol. Formaldehyde, alkylene glycol,
It is analyzed and quantified using methods such as gas chromatography and liquid chromatography.

In addition, when an elastomer is inserted into a linear polymer, the bond between the elastomer and polyacetal is broken, so
It becomes a telechelic elastomer having a hydroxyl group, a cal-I xyl group, and an amino group at the end.

Telekirik elastomers are precipitated from aqueous solutions. The precipitated nidistomer is analyzed and quantified using a conventional polymer analysis method.

The number average molecular weight of the acetal block copolymer of the present invention is ? It is the same as that of Riacetal, but it is generally between 10,000 and soo, oooO. The lower limit of the number average molecular weight is limited by the physical properties of the acetal block copolymer, and the upper limit is limited by the moldability of the acetal block copolymer. The number average molecular weight of the acetal block copolymer is determined by the following method. That is, when the number average molecular weight is 100,000 or less,
If the number average molecular weight is 100,000 or more, the weight average molecular weight determined by the light scattering method and the gel ξ-mision chromatography method (G, P , 0 method) to determine the number average molecular weight.

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

The acetal Zollock copolymer of the present invention is produced in the presence of a didistomer (hereinafter abbreviated as telekilic elastomer) having two functional groups selected from the group consisting of hydroxyl group, cardaxyl group, and amine group at the end of the polymer. It can be obtained by polymerizing formaldehyde, copolymerizing formaldehyde and a cyclic ether, or reacting polyoxymethylene with a cyclic ether.

Here, the telekirik elastomer functions as a molecular weight regulator during polymerization and reaction, and at the same time regulates the molecular weight of the polymer, it is inserted into the polymer as a solokic macromer.

The telechelic distomers used in the present invention are classified into the following four types.

The first is a styrene-based telescopic elastomer,
For example, polystyrene-polyzotadiene block copolymer (hydroxyl group end), polystyrene-hydrogenated polybutadiene block copolymer (hydroxyl group end), polystyrene-polyinoprene block copolymer (hydroxyl group end),
Examples include polystyrene-hydrogenated polyisoprene block copolymers (hydroxyl group terminals).

The second is an ester-based telekilic copolymer, such as polyethylene terephthalate-polyglobylene glycol block copolymer (hydroxyl group, carboxyl basic end), polyzotylene terephthalate-polytetramethylene glycol copolymer (hydroxyl group
, end), polyethylene/butylene terephthalate-polytetramethylene glycol zorosoc copolymer (hydroxyl group, cal-I xyl group end), etc.

The third type is an amide-based teleki elastomer, such as nylon-6-polypropylene glycol glock copoly-7-(terminated with amine group, carmexyl group), nylon-6-polyethylene adipate broth copolymer (terminated with cardaxyl group), nylon-6, 6-borisotylene succinate zolosoccopolymer (amino group terminal),
There is a nylon-6-polytetramethylene glycol block copolymer (amine Hong, all hydroxyl terminals) '4.

The fourth is lanthanum thread telekirik elastomer,
For example, 4,4'-diphenylmethane diisocyanate,
There are polyurethanes synthesized from tetramethylene glycol and polytetramethylene glycol, polyurethanes synthesized from 4,4'-dicyclohexylmethane diisocyanate, propylene glycol and polyzolopylene glycol, and the like.

Prior to polymerization and reaction, Telekilink elastomer is
It is desirable to purify it by methods such as washing, adsorption, and drying. Further, these elastomers can be used alone, or two or more kinds can be mixed and subjected to polymerization.

In the polymerization and reaction of the present invention, sufficiently purified formaldehyde, polyoxymethylene, and cyclic ether are used as starting materials for polyacetal.

Here, polyoxymethylene is a homopolymer of formaldehyde or trioxane, and has a number average molecular weight of 1.
0,000-500,000 preferably 30,000-
150,000.

The first group of cyclic ethers includes alkylene oxides represented by the general formula (aO: hydrogen, alkyl group, aryl group, each of which may be the same or different, m-2 to 6); There is.

Examples include ethylene oxide, propylene oxide, zotylene'oxy P1 epichlorohydrin, styrene oxide, oxetane, 3. '3-bis(chloromethyl)oxetane, tetrahydrofuran, oxenoξane, etc. Among these alkylene oxides, ethylene oxide is particularly preferred.

The second group of cyclic ethers includes cyclic formals represented by the general formula Ro, triethylene glycol formal, 1,4
- Zotanediol formal, l.

There are 5-bentanediol formal and 1,6-hexanediol formal. Among these cyclic formals, ethylene glycol formal, diethylene glycol formal and l.

4-butanedi and all-formal are preferred.

The cyclic ether is used in an amount of 0.0% per 100 parts by weight of the starting material.
0.3 to 100 parts by weight, and 0.1 to 50 parts by weight are used.

The anionic polymerization catalyst and cationic polymerization catalyst used in the polymerization/reaction of the present invention are the following compounds.

Typical groups of anionic polymerization catalysts include alkali metals such as sodium and potassium, alkali metal complex compounds such as sodium-naphthalene and potassium-anthracene, alkali metal hydrides such as +7um,
Alkaline earth metal hydrides such as calcium hydride, alkali metal alkoxides such as sodium methoxide and potassium 1-butoxide, alkali metal cardinates such as sodium caproate and potassium stearate, cardan such as magnesium caproate and calcium stearate. Acid alkaline earth metal salts, amines such as n-butylamine, diethylamine, trioctylamine, pyridine, quaternary ammonium salts such as ammonium stearate, tetrabutylammonium methoxide, dimethyldistearylammonium acetate, tetramethylphosphonium propionium ester, phosphonium salts such as trimethylbenzylphosphonium ethoxide, tributyltin chloride,
Examples include tetravalent organic tin compounds such as diethyltin dilaurate and dibutyltin dimethoxide, and alkyl metals such as n-dityllithium and ethylmagnesium chloride.

Examples of cationic polymerization catalysts include tin tetrachloride, tin tetrabromide, titanium tetrachloride, aluminum trichloride, zinc chloride, vanadium trichloride, antimony trifluoride, boron trifluoride, boron trifluoride diethyl etherate, and trifluoride. So-called Friedel compounds such as boron trifluoride coordination compounds such as boron acetic anhydrate and boron trifluoride triethylamine complex compounds
Kraft-type compounds, inorganic and organic acids such as perchloric acid, acetyl chlorate, hydroxyacetic acid, trichloroacetic acid, p-toluenesulfonic acid, triethyloquinium tetrafluoroborate, triphenylmethylhexa7
Examples include complex salt compounds such as 0-roantimonate, allyldiazonium hexafluorophosphate, allyldiazonium tetrafluoroselate, and alkyl metals such as quetylzinc, triethylaluminum, and diethylaluminum chloride.

These anionic polymerization catalysts and cationic polymerization catalysts are used in an amount of o,oos to 5 parts by weight based on 100 parts by weight of the starting material. The polymerization or reaction is carried out without solvent or in an organic medium.

The organic medium that can be used in the present invention is
-Aliphatic hydrocarbons such as hentane, n-hexane, n-hebutane, n-octane, cyclohexane, and cyclopentane, aromatic hydrocarbons such as benzene, toluene, silane, methylene chloride, chloroform, carbon tetrachloride, There are halogenated aliphatic hydrocarbons such as ethylene chloride and trichlorethylene, and halogenated aromatic hydrocarbons such as chlorobenzene. These organic media may be used alone or in combination of two or more. The nidistomer, 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 by experiment, depending on the molecular weight requirements of the desired acetal block copolymer.

The polymerization/reaction temperature is usually set between -20 and 230°C, but it is more preferably between 20 and 210°C when no solvent is used, and between -10 and 120°C when an organic medium is used.
Preferably between.

There are no particular restrictions on the polymerization/reaction time, but the time is between 5 seconds and 3 seconds.
00 minutes.

After a predetermined period of time has elapsed, a terminator is added to the reaction system to complete the polymerization or reaction. The obtained polymer is stabilized by removing unstable bed ends by hydrolysis or blocking unstable wood ends by a method such as esterification. The stabilized acetal block copolymer is put into practical use after the stabilizer and the like are cooled.

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

(1) The acetal block copolymer has extremely excellent toughness such as impact resistance and fatigue resistance, as well as strength and rigidity.

(2) By using a specific nidistomer, it is possible to impart performance similar to that of acetal zolock copolymer, and at the same time, the molecular weight of the polymer can be controlled arbitrarily. 7 The measurement items in the following examples are as follows.

Reduced viscosity 2 Polymer concentration 0.5 gr/di in p-chlorophenol/tetrachloroethane (1 part 1 weight ratio) solution
Measured value at 60℃.

Number average molecular weight (Mn): Value determined by the end group determination method and osmometry method of a polymer whose ends have been stabilized using acetic anhydride.

Izot impact value (notched): 0.25 parts of 2゜2-methylene-bis(4-methyl-6-tert-butylphenol) and polycaprolactam to 100 parts of the polymer that has been stabilized with wood ends using acetic anhydride. /polyhexamethyleneazide semi-Y/f 0.50 part of a terpolymer of Nananogukamido was added to the mixture using polyhexamethylene, and after mixing using a 50+ mφ extruder, flat plate molding was performed. This flat plate test piece was cut and measured according to ASTM D256. The larger the Izot impact value, the better the impact resistance.

Vibration fatigue characteristics: A test piece was cut from a flat plate and ASTMD
20℃, 1800 repeated vibration cycles according to 671
Measured in times/minute. The maximum stress that does not cause the specimen to break when subjected to repeated vibrations of 10 times - fatigue strength is used as an index of fatigue resistance. The higher the fatigue strength, the better the fatigue resistance.

Book strength: Cut a test piece from a flat plate, AS1'MD63
Measured according to 8. The higher the tensile strength, the better the strength and rigidity.

Example (1) Production method of acetal block copolymer Purity 99
．． 9% formaldehyde gas per hour p 1 , o
o parts (hereinafter parts indicate parts by weight) of polystylene terephthalate-polytetramethylene glycol block copolymer (hereinafter referred to as PB'r-PTG) at a ratio of 60.2 gr/l as a molecular weight regulator. abbreviation), 3.5 X 10”” mol/I! as a polymerization catalyst. The mixture was continuously fed into 500 parts of toluene containing dibutyltin dilaurate for 3 hours.

The telekirik elastomer used here as a molecular tFA moderator was synthesized from the following raw materials and had a number average molecular weight of 2. I
It is a polymer having X ton, hydroxyl group, and carboxyl group at the end.

Tetramethylene glycol terephthalate, 1? Litetramethylene glycol (Mn 1,25
0) Toluene containing PBT-PTG and a polymerization catalyst at the above concentration was also continuously supplied at a rate of 500 parts/hr for 3 hours, and the polymerization temperature was maintained at 62° C. during this period. The polymer was separated from toluene, washed and dried, and 398 parts of the polymer was removed.

After acetylating this polymer, in benzyl alcohol,
Although the extraction operation was performed at 60°C for 5 hours, unreacted PBT-
No PTG was extracted. From this, PBT-
It became clear that all the PTO was inserted into the polymer.

(2) Confirmation of the structure of the acetal block copolymer (
5 parts of the polymer obtained in 1) were dispersed in 95 parts of a 0.3N @ acid aqueous solution and heated at 80°C for 3 hours. Through this hydrolysis operation, all of the polyacetal consisting of oxymethylene chains returned to formaldehyde.

On the other hand, PBT-PTG only undergoes slight hydrolysis under these conditions. The acidic aqueous solution was neutralized with a 0.5N aqueous sodium hydroxide solution, and then the elastomer precipitated in the aqueous solution was separated and dried, and 1.75 parts of nidistomer was recovered. The load n of this elastomer was 2.0×104 according to the terminal group determination method, and the Mn of the elastomer used in the polymerization reaction of Habo (1) was maintained.

After acetylating the polymer obtained in (1), terminal group analysis and determination using perfusion and external radiation absorption spectra revealed that all the terminal groups were acetyl groups, and acetyl group/CH2O chain = 153X10-5 mol/ The mol value was obtained.

From this fact, it became clear that 11 in the polyacetal portion of the polymer (1) was 3.9 x 10'.

From the above analysis results, the polymer obtained in (1) is a mixture of the following two types of polymers.

prisoner HO+0H20h drunkenness X, -(aH2o9l-1,9
9% by weight (B) Ho, 4-0H20 fH1% by weight
(Here, Xl is PBT-PTG and is composed of the following soft segment and hard segment.

0 0 Also, C represents 1 to 1299. ) Of the two types of polymers mentioned above, (B) is a polymer based on a nidistomer added as a molecular weight regulator, and (B) is a polymer based on a trace amount of water present in the polymerization system. Further, the content of the nidistomer component in this polymer was 35% by weight.

(3) Measurement of physical properties of acetal block copolymer (1)
The reduced viscosity of the polymer obtained in ) was 2.85, which was a desired value. 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.

Izotsu impact value 65y4・cwr/c
m fatigue strength 280 Kg/α2 tensile strength
61 s Kq /cm2 Thus, this block copolymer is excellent in both toughness and strength/rigidity.

Example 2 (4) Production method of acetal block copolymer Formaldehyde: 100 parts/h [, ethylene oxide: 2.2
64. parts/hr as a molecular weight regulator. Ogr/
l! The mixture was continuously fed into 500 parts of toluene containing nylon 6-polypropylene glycol block copolymer (hereinafter referred to as NY-PPG) for 5 hours.

The telekirik elastomer used here as a molecular weight regulator had a number average molecular weight of 1.3X synthesized from the following raw materials.
10', an amine group, and a carzexyl group at the end.

Prepolymer made by reacting polypropylene glycol and adipic acid (Mntsso) ε-caprolactam polymer (nylon-6, Mn1170) Toluene containing NY-PPG at the above concentration is also 500
It was continuously supplied for 5 hours at a rate of 1 part/hr.

In addition, as polymerization catalysts, tetrazotylammonium acetate and boron trifluoride dibutyl etherate were each used at 0.00.
3 parts/hr and 0.08 parts/hr were continuously fed through four separate tubes for 5 hours, and the polymerization temperature was maintained at 60° C. during this time. The polymer was separated from toluene, then washed and dried to obtain 688 parts of polymer.

After acetylating this polymer, in benzyl alcohol,
Although the extraction operation was performed at 60°C for 5 hours, unreacted NY-P
No PG was extracted. From this, NY-PPG
It became clear that all were inserted into the polymer.

(5) d44 of the structure of acetal block copolymer
g.

The polymer obtained in (4) was hydrolyzed under the same conditions as in Example 1, and the insertion rate of oxyethylene units in this polymer was 1.50.
The result was mol/100 mol.CH2O chain.

On the other hand, NY-PPG undergoes only slight hydrolysis under these conditions. In the same manner as in Example 1, 1.3 parts of elastomer was recovered from an aqueous solution. The Mn of this nidistomer was found to be 1.2×10′ according to the end group determination method.

After acetylating the polymer obtained in (4), end group analysis and quantitative analysis revealed that total end groups/0H20 chain = 171X
1 (1'''5 mol/mol). From this fact, it became clear that the Ml of the d IJ acetal part of the polymer (4) was 3.5 X to'.

From the above analysis results, the polymer obtained in (4) is mainly composed of a polymer having the following structure.

(C1, IO-[-+0H20 Sunday "10H201 (20
X2+CH2Ote0H20H20te11 (Here, X2 is NY-PPG and is composed of the following soft segment and hard segment.

Further, d represents 1 to 1669, and e represents 1 to 16. ) The elastomer component content of this polymer is 26% by weight.

(6) Measurement of physical properties of acetal block copolymer (4
The reduced viscosity of the polymer obtained in ) was 2.45, which was almost equal to the expected value. Furthermore, the five-point properties of molded articles of this polymer are as follows.

Izotsu impact value 67 edge/(7)/Cnt fatigue strength 290~/crn2 tensile strength
603 K (77 cm2) This Zoroku copolymer is also excellent in both toughness and strength and rigidity.

Margin below (7) Production method of acetal block copolymer Polyoxymethylene dino hydroxide having a reduced viscosity of 2.95 and sufficiently dried under reduced pressure, 5.02 Kp, 1. Ethylene glycol formal 420gr.

Polystyrene-hydrogenated polybutadiene block copolymer (abbreviated as PSt-PBD under tlu) as molecular weight modifier) 3.40 to 9. Cyclohexa ysoKy was charged into the reaction tank. Molecule here! The telechelic elastomer used as a modifier was synthesized by polymerizing shibutadiene by a living polymerization method, adding styrene, and then adding ethylene oxide, and then hydrogenated it with a number average molecular weight of 3.0 x 10.
4. It is an elastomer with a hydroxyl group terminal.

After charging, the contents of the reaction tank were heated to 70°C.

1.25 g of boron trifluoride (dibutyl nitrate) in the reaction tank
One reaction was started by adding r.

After maintaining the internal temperature of the reaction tank at 70°C for 32 minutes,
The reaction was stopped by adding 550 gr of cyclohexane containing 550 gr of tributylamine. After the polymer was separated by filtration, it was washed five times with a large amount of methanol, and a polymer of s and 39xy was recovered.

PS can also be obtained by hot benzyl alcohol extraction of this polymer.
t-PBD could not be detected at all. From this point, Pst
- It became clear that all PBDs were inserted into the polymer.

(8) Confirmation of the structure of the acetal block copolymer (
The obtained polymer was hydrolyzed under the same conditions as in Example 1, and the insertion rate of oxyethylene units in this polymer was found to be 1.53 mol/100 mol/CH2O chain.

On the other hand, PSt-PBD is not hydrolyzed at all under these conditions. Use the same method as Example 1 to prepare an aqueous solution! 11.7 parts per liter of elastomer was recovered. The Mn of this elastomer is
The molecular weight was 3.0×104, which coincided with the molecular weight of the telekirik elastomer used as the molecular weight regulator.

(After acetylating the polymer obtained by force, quantitative analysis of the terminal groups revealed that total terminal groups/CH2O chain=103
A value of 10-5 mol/mol was obtained. This fact (7)
) The Mn of the polyacetal part of the polymer is 5.8×104
It became clear that.

From the above analysis results, the polymer obtained in (7) is mainly composed of a polymer having the following structure.

(Here, X3 is PSt-PBD and is composed of a soft segment and a hard segment below.

- to'H2 (:&-cHz-CH2+ Soft segment unit + CHt CH+ 1 HzCHa Also, f is 1 to 1939.g is 1 to 29.) The elastomer component content of this polymer is 34% by weight. .

(9) Measurement of physical properties of acetal block copolymer (reduced viscosity of the polymer obtained by force is 3.83, which is equal to the initially set value. Also, the physical properties of the molded product of this polymer are as follows. This is the general rule.

Izot impact value 56 to 2°crn/
crn fatigue strength 270Ky/c
dl tensile strength 613 to 51/
d This block copolymer is also a polymer that is excellent in both toughness, strength, and rigidity.

Comparative Example 1 (10) Production of polyacetal Instead of the telescopic elastomer used in Example 1,
Polytetramethylene glycol (¥/1n7.200)
20. All samples were as in Example 1 except that a concentration of Ogr/L was used.
320 parts of a polymer was obtained by the same procedure as above.

01) Confirmation of the structure of polyacetal The structure of the polymer obtained in (10) was analyzed using the same method as in Example 1, and the following results were obtained.

(g)HO(CH+0h11+(CHz) 4QtCH
20 trench H60 weight mooring) HO hand (CH2) a O+-
A-c H20 beats-H39 weight% Zo0
1310 (G) Ho+CH, 0≠−H1 weight ratio 310 (Here, h indicates 1 to 1309) Among the above three types of polymers (g)), Ho is a polymer based on polytetramethylene glycol. p, (G) is a water-based polymer that was present in a trace amount in the polymerization system.

(12) Measurement of physical properties of polyacetal The physical properties of the polymer obtained in 0■ are as follows.

Izot impact value: 8.8 to 9φcm Secondary fatigue strength: 130 to non-tensile strength: 310 Ky/7 Although the Izot impact value of this polymer has been slightly improved, the fatigue resistance and strength/rigidity have significantly decreased. It is a polymer that lacks good mechanical properties.

Same, polyoxymethylene polymer HO+CH, O juice-H 1:110 The physical properties of the molded product obtained are as follows.

Izotsu impact value 6.8 to 2 crr1
/crn fatigue strength 33 oKy
/i tensile strength 720 L9/c
d Examples 4 to 9 Acetal block copolymers shown in Table 1 were produced using the starting materials and elastomers (molecular weight modifiers) shown in Table 1. All of these polymers are new polymers. Table 1 also shows the physical property values of these polymers.

In all Examples, polymers having both excellent toughness, strength, and rigidity were obtained.

Comparative Examples 2 to 3 Block copolymers shown in Table 1 were produced using starting materials and polymers having active hydrogen atoms as shown in Table 1. A block copolymer of formaldehyde and a polymer having an active hydrogen atom does not have sufficient improvement in toughness and has a significant decrease in strength and rigidity.

(Hereafter, remainder f3) Procedural amendment trace (spontaneous) Mr. Kazuo Wakasugi, Director General of the Special Preparation Agency, February 1982, 1982 Patent Application No. 47114
No. 2 Name of the invention New acetal block copolymer and its production method a Relationship with the case of the person making the amendment Patent applicant 1-2-6 Dojimahama, Kita-ku, Osaka-shi, Osaka (003)
Teru Miyazaki, President and Representative Director of Asahi Kasei Industries, Ltd. 4 Column 5 of “Claims” and “Detailed Description of the Invention” of the specification to be amended, Contents of the amendment (1) “On pages 1 to 5 of the specification” “Claims”
Please make corrections as shown in the attached sheet.

(2) In the second line from the bottom of page 9, "Allyl group is selected," is corrected to "Aryl group is selected."

(3) "Oxytetramethylene unit (-(OH2)40-) is particularly preferred." on page 10, lines 14-15 of the same page is replaced with "oxytetramethylene unit (-(OH2)40-)."
0-)%. ” is corrected.

(4) On page 13, line 16, "4,4-diphenylmethane diisocyanate" is corrected to "'t+4") phenylmethane diisocyanate."

(6) On page 15, line 3, “Allyl group is selected,
" is corrected to "Aryl group is selected."

(7) Page 15, line 11 [(1), (2)
, (5) and (6)" is corrected to "Acetal block expressed in (1), (2) and (5)-c table b."

(8) "(2) and (6) that still have acetal copolymers at both ends" on page 16, lines 1 and 2 are changed to [
! ! (2) with acetal copolymer at both ends is d
Correct.

(9) On page 17, lines 14-15, "using the terminal group assay method" is corrected to "using the terminal group assay method."

00) On page 19, lines 4 to 5, "The second is an ester telelink block cobolimer" was replaced with "the second
is an ester-based telechelic elastomer,” K corrects.

Ql) In page 33, line 18 of the same, [Mn of the mer is 1.2X10' according to the terminal group determination method] is replaced with ``Mn of the mer is 1.2
According to the terminal group method, n is corrected to 1.2×10′.

α2 Same page 34 line 11 Ru.

(13) “NH+ (OH2
)4 ONH+1oj to 1 (14) ``Table 1'' on page 42 of the same page is attached to ``Table 1''.
Correct the table.

Claims (1) It has a structure in which an elastomer having a secondary transition temperature of -120 to +40'c is inserted into the main chain of a linear polymer, and the number average molecular weight is io, ooo to A novel acetal block copolymer (2) composed of an acetal polymer and an elastomer having a molecular weight of between 500,000 and 400,000.Claims in which the acetal polymer is an acetal homopolymer composed of repeating oxymethylene units←0H20) Copolymer (3) according to item 1, wherein the acetal polymer is a polymer consisting of repeating oxymethylene units.
: Selected from hydrogen, an alkyl group, and an aryl group, each of which may be the same or different.

The copolymer (4) according to claim 1, which is an acetal copolymer having a structure in which m = 2 to 6) is inserted.The oxyalkylene unit is an oxyethylene unit 'c (OH2)20-). Claim 1
Copolymer (5) according to claim 1 or 3 The copolymer (6) according to claim 1 or 3, wherein the oxyalkylene unit is an oxytetramethylene unit (OH2)40'3 ) The copolymer (7) according to claim 1, in which the elastomer is styrene-based nylastomerched.
Copolymer (8) according to claim 1, which is a styrene-based nilast marker, a polystyrene-polybutadiene block copolymer, or a polystyrene-hydrogenated polybutadiene block copolymer (8) A patent in which the elastomer is an ester-based elastomer The copolymer (9) according to claim 1, wherein the ester elastomer is a polybuterene terephthalate-polytetramethylene glycol block copolymer or a polyethylene-butylene terephthalate-boridetramethylene glycol block copolymer. Copolymer (11) according to claim 1, wherein the elastomer is an ami-P elastomer (11) The copolymer according to claim 1, wherein the elastomer is an ami-P elastomer. ,t? Lipropylene glycol block copolymer or nylon
6-polytetramethylene glycol block copolymer according to claim 1 or 10; copolymer glycol and polyester according to claim 1, wherein the elastomer is a urethane-based elastomer; Claim 1, which is a polyurethane synthesized from tetramethylene glycol, is still a copolymer according to claim 12. Claims, in which the content of the elastomer component in the linear polymer is 0.5 to 50% by weight In the copolymer described in Scope 1, formaldehye F is polymerized in the presence of an elastomer having two functional groups selected from the group consisting of a hydroxyl group, a calixyl group, and an amine group at the end of the polymer. A method for producing a novel acetal block copolymer characterized by (161) in the presence of an elastomer having two functional groups selected from the group consisting of a hydroxyl group, a carxyl group, and an amine 7 group at the end of the polymer. , a method for producing a novel acetal block copolymer characterized by copolymerizing formaldehyde and a cyclic ether (17) Two groups selected from the group consisting of a hydroxyl group, a caldecyl group, and an amide group at the terminals of the polymer. A method for producing a novel acetal block copolymer characterized by reacting polyoxymethylene with a cyclic ether in the presence of an elastomer having a functional group.Claim 16 or 1, wherein the cyclic ether is ethylene oxide. The method for producing eel according to item 17, wherein the cyclic ether is ethylene glycol hydrated marl,
Amendment to the manufacturing process described in claim 16 or 17 (voluntary), which is a compound selected from the group consisting of diethylene glycol formal and 1°4-butanediol formal. Director Kazuo Wakasugi 1 Case Description 1981 Patent Application No. 47114
No. 2 Name of the invention New acetal block copolymer and its manufacturing method & Relationship with the person making the amendment Patent applicant 1-2-6-4 Dojimahama, Kita-ku, Osaka-shi, Osaka Prefecture Subject of the amendment & Contents of the amendment ( 1) Correct the 11th line on page 34 of Book 1 of Mingqi.

that's all

Claims (1)

Scope of Claims: (1) Has a structure in which an elastomer having a secondary transition temperature of -120 to +40°C is inserted into the main chain of a linear polymer, and has a number average molecular weight of 10,000 to 500. A novel acetal block copolymer composed of an acetal polymer and an elastomer between . Copolymer (3) according to item 1, in which the acetal polymer is composed of repeating oxymethyleff units, in which oxydialkyl (Ro:
It is selected from hydrogen, an alkyl group, and an allyl group, and each may be the same or different. The copolymer (4) according to claim 1, which is an acetal copolymer having a structure in which m-2 to m-6) is inserted.The copolymer (4) according to claim 1, which is an acetal copolymer having a structure in which m-2 to m-6) is inserted. Copolymer (5) according to claims 1 and 3, wherein the oxypurkylene unit is oxytetramethylene unit + (0H2)40+ Claim 1
Copolymer (6) according to Claims 1 and 3, wherein the nydistomer is a styrene dystomer; Claim 1, wherein the copolymer (7) styrenic elastomer is a polystyrene-polyzotadiene block copolymer or polystyrene. - The copolymer (8) according to claims 1 and 6, which is a hydrogenated polyzotadie/f-lock copolymer. ) The copolymerization system according to claim gt and claim 8, wherein the ester-based nilastone is a polygtylene terephthalate-polytetramethylene glycol block copolymer or a polyethylene butylene terephthalate-polytetramethylene glycol block copolymer. The copolymer according to claim 1, which is an amide elastomer, is a nylon-6-polypropylene glycol block copolymer or a nylon-6-polytetra, methylene glycol block copolymer. The copolymer according to claim 1, wherein the elastomer is a urethane elastomer. The copolymer according to claim 1, wherein the urethane elastomer is 4,4-diphenylmethane diisocyanate, tetramethylene glycol. and the copolymer (b) according to claims 1 and 12, which is a polyurethane synthesized from polytetramethylene glycol.
The content of the nidistomer component in the linear polymer is 0.5 to 50
% by weight of the copolymer according to claim 1. In the presence of an elastomer carrying two functional groups selected from the group consisting of hydroxyl group, carboxyl group, and amino group at the end of the polymer. A method for producing a novel acetal block copolymer characterized by polymerizing formaldehye P (2) Two functional groups selected from the group consisting of hydroxyl group, carboxyl group, and amino group on the wood end of the polymer A method for producing a novel acetal block copolymer characterized by total copolymerization with formaldehyde and a cyclic ether in the presence of a distomer having
A novel method for producing an acetal block copolymer characterized by reacting polyoxymethylene with a cyclic ether in the presence of an elastomer having two functional groups selected from the group consisting of amino groups. The process according to claim 16 or 17, wherein the ether is ethylene oxide (selected from the group consisting of The manufacturing method according to claim 16 or 17, which is a compound obtained by