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CN102177186A - Production method of modified polyacetal resin having hydroxyl group - Google Patents

Production method of modified polyacetal resin having hydroxyl group Download PDF

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Publication number
CN102177186A
CN102177186A CN2008801314687A CN200880131468A CN102177186A CN 102177186 A CN102177186 A CN 102177186A CN 2008801314687 A CN2008801314687 A CN 2008801314687A CN 200880131468 A CN200880131468 A CN 200880131468A CN 102177186 A CN102177186 A CN 102177186A
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polyacetal resin
modified polyacetal
hydroxyl
compound
group
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CN102177186B (en
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久保田丰
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Polyplastics Co Ltd
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Polyplastics Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
    • C08G2/30—Chemical modification by after-treatment

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  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
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Abstract

The present invention provides an extremely effective decomposition treating agent, treatment conditions, and the like for producing a hydroxyl group-containing modified polyacetal resin. Specifically, a modified polyacetal resin (a 1) having an ester-bonded side chain is prepared, and the modified polyacetal resin (a 1) is heat-treated in the presence of a hydrolysis-treating agent selected from a quaternary ammonium compound and a basic heterocyclic compound to hydrolyze the ester bond to form a hydroxyl group.

Description

Manufacture method with modified polyacetal resin of hydroxyl
Technical field
The present invention relates to import effective manufacture method of the modified polyacetal resin of hydroxyl.Further specifically, relate to the manufacture method of the modified polyacetal resin that contains hydroxyl, comprise that preparation has the modified polyacetal resin of the side chain that has formed ester bond, this modified polyacetal resin utmost point is hydrolyzed effectively handles and the formation hydroxyl.
Background technology
Polyacetal resin is excellent on the balance of mechanical properties, chemical proofing, sliding etc., and because its handling ease, pretend for representative operation plastics be that the center is subjected to extensive utilization with various mechanical parts such as electrical and electronic parts, trolley parts.But,, further required singularity as the character of its material is also many along with the field that utilizes polyacetal resin enlarges.
Usually, the crystallinity height of polyacetal resin, minimum with the affinity or the intermiscibility of other material.Therefore, be difficult to also be difficult to improve simultaneously adaptation with coating, printing-ink, colouring matter or binding agent etc. by carrying out modification with compoundization of other resin material, additive, filling agent etc.For example, when improving shock-resistance co-blending elastic body etc., since poor with elastomeric affinity and intermiscibility, so can't give the HI high impact characteristic.In addition, because of the dispersed bad sur-face peeling that causes molding of elastomerics etc., significantly damage the outward appearance of molding.And then, when being added into additives such as stablizer, lubricant in the polyacetal resin, then there is additive to separate to ooze out into the surface of molding and damages the outward appearance on surface for modification, can not effectively utilize the problem of the function etc. of additive simultaneously.Therefore, the purposes of polyacetal resin is subjected to bigger restriction more.
In order to improve the affinity of polyacetal resin, effectively in polyacetal resin, import suitable functional group, as wherein a kind of, can enumerate the modified polyacetal resin that has imported hydroxyl.This type of modified polyacetal resin that contains hydroxyl have improve with glass be inorganic filling material adaptation, improve effect such as physical strength, especially, the modified polyacetal resin that side chain has hydroxyl is effective.
Imported the modified polyacetal resin of hydroxyl in the above-mentioned side chain, in the manufacturing of the known polyacetal resin that utilizes cationoid polymerisation in the past, the reactive compounds that can contain hydroxyl by use is as the comonomer preparation that becomes to assign to, but in this polyreaction, the reactive compounds that contains hydroxyl also works as chain-transfer agent, so the polyacetal resin of gained becomes and has branched structure, in addition, the molecular weight that also becomes easily is insufficient.For preventing this type of chain transfer reaction; the method of ideal is that the hydroxyl of this reactive compounds is supplied in polymerization with the protection of protecting groups such as ethanoyl again; using basic cpd etc. to carry out multipolymer behind the preparation multipolymer must handle; protect hydroxyl protecting group deprotection and form hydroxyl, but find as yet to be used for the protecting group of protection hydroxyl deprotection and form the treatment process of hydroxyl effectively.
Should illustrate, to handle with basic cpd through the modified polyacetal resin of glycerol formal or its ester derivative modification though put down in writing among the JP A 3 47818, but its main purpose is to remove the unstable end group of modified polyacetal resin, the hydrolysis that utilizes ester group is formed hydroxyl there is no record, in addition, the processing that utilizes basic cpd disclosed herein for purpose of the present invention, can not realize sufficient hydrolysis effect.In addition; among WO A 98/42781 and the JP A 2,006 299107; when disaggregating treatment, use quaternary ammonium compound though disclose the unstable terminal part of polyacetal resin with unstable terminal part, to the present invention as the treatment process of purpose, promptly, to as mentioned above with the protecting group deprotection of modified polyacetal resin and the method for hydrolysis that forms hydroxyl there is no any record.
Summary of the invention
The object of the present invention is to provide the effective manufacture method of the modified polyacetal resin that has imported hydroxyl, more specifically, purpose is to be provided for preparing the modified polyacetal resin with the side chain that has formed ester bond, this modified polyacetal resin is hydrolyzed handles and make extremely effectively the disaggregating treatment agent or the treatment condition etc. of the modified polyacetal resin that contains hydroxyl.
The inventor etc. further investigate repeatedly in view of above-mentioned problem, found that, the modified polyacetal resin that has the side chain that has formed ester bond by preparation, this modified polyacetal resin is heat-treated in the presence of the hydrolysis treatment agent that is selected from quaternary ammonium compound and alkaline heterogeneous ring compound, can realize high percent hydrolysis and solve above-mentioned problem, thereby finish the present invention.
Promptly, the present invention is the manufacture method of modified polyacetal resin (A) with hydroxyl, it is characterized in that, preparation has the modified polyacetal resin (A1) of the side chain that has formed ester bond, in the presence of the hydrolysis treatment agent that is selected from quaternary ammonium compound and alkaline heterogeneous ring compound, this modified polyacetal resin (A1) is heat-treated, make ester linkage hydrolyzing and form hydroxyl.
Detailed Description Of The Invention
Below, the present invention is described in detail.The invention is characterized in, preparation has the modified polyacetal resin (A1) of the side chain that has formed ester bond, this modified polyacetal resin (A1) is heat-treated in the presence of the hydrolysis treatment agent that is selected from quaternary ammonium compound and alkaline heterogeneous ring compound, can realize the manufacturing of the modified polyacetal resin that contains hydroxyl (A) of high percent hydrolysis whereby.
Among the present invention,, can use the compound that is selected from quaternary ammonium compound and alkaline heterogeneous ring compound as the hydrolysis treatment agent.
The available quaternary ammonium compound is not particularly limited among the present invention, and as preferred quaternary ammonium compound, it is represented to enumerate following formula (1), and they also can a plurality ofly be used in combination.
[R 1R 2R 3R 4N +] nX n (1)
(in the above-mentioned formula, R 1, R 2, R 3, R 4Independent separately, the alkyl of expression carbonatoms 1 ~ 20, this alkyl is straight or branched alkyl, cycloalkyl, aryl, aralkyl or alkylaryl.Alkyl can have substituting group, and substituent kind is hydroxyl, acyl group, acyloxy, alkoxyl group, alkoxy carbonyl, carboxyl, amino, amide group, vinyl, allyl group, hydroxyalkyl oxygen base, alkoxyalkyl oxygen base and halogen atom.X nThe expression hydroxyl or derive from the compound that is selected from following (i) ~ (ix) with the salifiable negatively charged ion of quaternary ammonium shape.N represents the integer more than 1.N [R 1R 2R 3R 4N +] can be different mutually.)
(i) organic thioic acid sulfoacid of the carboxylic acid of carbonatoms 1 ~ 20, hydracid, oxygen acid, inorganic thioic acid sulfoacid or carbonatoms 1 ~ 20
(ii) acid ring-type amide compound
(iii) poly carboxylic acid
(iv) aminocarboxylic acid
(v) carbonic acid monoesters and/or hydrogen-carbonate metal-salt
(vi) acid enol based compound
(vii) phenol based compound and/or pure based compound
(viii) acid azole compounds
(ix) be selected from the non-carboxylic acid based compound of organosulfur compound, organo phosphorous compounds and organoboron compound.
Quaternary ammonium compound is so long as represented then being not particularly limited of above-mentioned general formula (1).For example, can enumerate tetramethyl-ammonium, tetraethyl ammonium, tetrapropyl ammonium, the tetra-n-butyl ammonium, ethyl trimethyl ammonium, the oxypropyl trimethyl ammonium, cetyltrimethyl ammonium, the tetradecyl trimethyl ammonium, 1,6 hexa-methylene two (trimethyl ammonium), decamethylene two (trimethyl ammonium), (3 chlorine, 2 hydroxypropyls) trimethyl ammonium, (2 hydroxyethyl) trimethyl ammonium, (2 hydroxyethyl) triethyl ammonium, (2 hydroxyethyl) tripropyl ammonium, (2 hydroxyethyl) three normal-butyl ammoniums, (2 hydroxyethyl) methyl diethyl ammonium, (2 hydroxypropyl) trimethyl ammonium, (2 hydroxypropyl) triethyl ammonium, (3 hydroxypropyl) trimethyl ammonium, (3 hydroxypropyl) triethyl ammonium, (4 hydroxybutyl) trimethyl ammonium, (4 hydroxybutyl) triethyl ammonium, diallyl dimethyl ammonium, tri methyl benzyl ammonium, the triethyl hexadecyldimethyl benzyl ammonium, the tripropyl hexadecyldimethyl benzyl ammonium, three normal-butyl hexadecyldimethyl benzyl ammoniums, the trimethylphenyl ammonium, triethyl phenyl ammonium, two (2 hydroxyethyl) Dimethyl Ammonium, two (2 hydroxyethyl) diethyl ammonium, two (2 hydroxypropyl) Dimethyl Ammonium, two (2 hydroxypropyl) diethyl ammonium, three (2 hydroxyethyl) ammonium methyl, three (2 hydroxyethyl) ethyl ammonium, three (2 hydroxypropyl) ammonium methyl, three (2 hydroxypropyl) ethyl ammonium, three (2 hydroxyethyl) octadecyl ammonium, four (hydroxymethyl) ammonium, four (methoxymethyl) ammonium, four (2 hydroxyethyl) ammonium, four (2 hydroxypropyl) ammonium, (poly-(oxyethane)) trimethyl ammonium, (poly-(propylene oxide)) trimethyl ammonium, (poly-(oxyethane)) triethyl ammonium, the oxyhydroxide of quaternary ammoniums such as (poly-(propylene oxide)) triethyl ammonium, or above-mentioned quaternary ammonium and the formed quaternary ammonium salt of negatively charged ion that derives from the compound that is selected from aforementioned (i) ~ (ix).
As the compound that belongs to aforementioned (i) that forms quaternary ammonium salt, can enumerate hydracids such as hydrochloric acid, bromic acid, oxygen acid such as sulfuric acid, nitric acid, phosphoric acid, thioic acid sulfoacids such as thiosulfuric acid, carboxylic acids such as formic acid, acetate, propionic acid; As belonging to aforementioned acid ring-type amide compound (ii), can enumerate (different) cyanuric acid, phthalic imidine etc.; As belonging to aforementioned poly carboxylic acid (iii), can enumerate 1,2,3,4 ethylene-dimalonic acids or be (copolymerization) polymkeric substance of forming of constituent etc. with the unsaturated monomer that vinylformic acid, methacrylic acid etc. contain carboxyl; As belonging to aforementioned aminocarboxylic acid (iv), can enumerate nitrilotriacetic acid(NTA), ethylenediamine tetraacetic acid (EDTA) etc.; Aforementioned (carbonic acid monoesters v) and/or hydrogen-carbonate metal-salt can be enumerated carbonic acid monomethyl ester, hydrogen-carbonate calcium salt etc. as belonging to; Aforementioned (acid enol based compound vi) can be enumerated methyl ethyl diketone, methyl aceto acetate etc. as belonging to; Aforementioned (phenol based compound vii) and/or pure based compound can be enumerated dihydroxyphenyl propane, Resorcinol etc. as belonging to; Aforementioned (acid azole compounds viii) can be enumerated theophylline, benzoglyoxaline etc. as belonging to; As the non-carboxylic acid based compound that is selected from organosulfur compound, organo phosphorous compounds and organoboron compound that belongs to aforementioned (ix), can enumerate methylsulfuric acid, methylsulfonic acid, dimethyl phosphonic acids, phenyl-boron dihydroxide etc.For quaternary ammonium with as the sour residue or the negatively charged ion of the compound of above-mentioned (i) ~ (ix) form the formed quaternary ammonium salt of residue, among WO A WO98/42781, JP A 2,006 257166, JP A 2,006 282836, the JP A 2,006 299107 detailed disclosing arranged, also can use above-mentioned quaternary ammonium salt among the present invention.
In the represented quaternary ammonium compound of aforementioned formula (1), n is the integer more than 1.When the X of the balance anion of formation quaternary ammonium compound was poly carboxylic acid, n was generally more than 4, and the X that forms balance anion is the situation outside it, and n is generally 1 ~ 3.
In addition, among the present invention, can be used as the alkaline heterogeneous ring compound that other hydrolysis treatment agent uses and also be not particularly limited, but preferably can enumerate 1,8 diazabicyclo [5.4.0] Shi one Tan Xi 7,1,5 diazabicyclo [4.3.0] Ren Xi 5.
Among the present invention, as the quaternary ammonium compound of hydrolysis treatment agent use or the usage quantity of alkaline heterogeneous ring compound, forming ester group amount (mol) with respect to the side chain with modified polyacetal resin (A1) of the side chain that has formed ester bond described later is 0.1 ~ 1000 equivalent, preferred 5 ~ 500 equivalents, preferred especially 10 ~ 300 equivalents.Then effect is insufficient for less than 0.1 equivalent, and when surpassing 1000 equivalents, and then the modified polyacetal resin that contains hydroxyl (A) of gained can variable color, so all not preferred.
Then, be elaborated for the modified polyacetal resin with the side chain that has formed ester bond (A1) that uses among the present invention.The present invention prepares the modified polyacetal resin (A1) with the side chain that has formed ester bond as previously mentioned, (A1) heat-treats in the presence of aforementioned hydrolysis treatment agent with this modified polyacetal resin, ester linkage hydrolyzing obtained having the modified polyacetal resin (A) of hydroxyl.
Among the present invention, above-mentioned preparation method with modified polyacetal resin (A1) of the side chain that has formed ester bond is not particularly limited, but as preferred manufacturing procedure, can enumerate three
Figure 899995DEST_PATH_IMAGE001
Alkane (a), the hydroxyl of polymerizable compound that is selected from the compound (b) of cyclic ether with hydroxyl and cyclic formal and has a hydroxyl are by acylations or silylanizing and the method that protected compound (c) carries out copolymerization.
Here, use in the preparation of above-mentioned modified polyacetal resin (A1) three
Figure 172845DEST_PATH_IMAGE001
Alkane (a) is meant the cyclic trimer of formaldehyde, can make formalin reaction usually and get in the presence of an acidic catalyst, can be with it with methods such as こ distillation purification use.
Then, the cyclic ether that being selected from of using in the preparation as above-mentioned modified polyacetal resin (A1) do not have hydroxyl and the compound (b) of cyclic formal, can enumerate oxyethane, 1,3 dioxolane, 1,4 butyleneglycol methylal, glycol ether methylal as preferred compound.
Compound (b) is not the necessary composition that utilizes in the preparation of the modified polyacetal resin with side chain (A1) of ester bond, with respect to three 100 moles in alkane (a), its ratio can be 0 ~ 30 mole, then preferably uses as copolymer composition when considering the thermostability etc. of gained modified polyacetal resin, its ratio is preferably with respect to three Alkane (a) is 0.05 ~ 30 mole for 100 moles, more preferably with respect to three
Figure 416241DEST_PATH_IMAGE001
Alkane (a) is 0.1 ~ 20 mole for 100 moles.
Then; the hydroxyl of the polymerizable compound with hydroxyl that uses in the preparation as above-mentioned modified polyacetal resin (A1) is by acylations or silylanizing and protected compound (c); can enumerate with cyclic formal, the glycidyl ether that contains hydroxyl, the trimethylene oxide that contains hydroxyl that contain hydroxyl, the vinyl compound that contains the vinylbenzene of hydroxyl and contain hydroxyl as the polymerizable compound that contains hydroxyl acylations or silylanizing and the protected compound of its hydroxyl by formyl radical, ethanoyl etc. as preferred examples.
Particularly, as polymerizable compound, can enumerate glycerol formal, TriMethylolPropane(TMP) methylal, trimethylolethane methylal, 5,5 dihydroxyl methyl 1,3 two with hydroxyl Alkane, 5 hydroxyls 1; 3 Dioxepanes, Racemic glycidol, 3 ethyls, 3 hydroxymethyl trimethylene oxide, 3; 3 dihydroxyl methyl trimethylene oxide, o-hydroxy ethene, a hydroxy styrenes, para hydroxybenzene ethene etc., its hydroxyl are by acylations or silylanizing and protected compound can be illustrated as aforesaid compound (c).
Among the present invention; when preparation has the modified polyacetal resin (A1) of the side chain that has formed ester bond; viewpoints such as importing rate from the easiness of its molecular weight control, polymerization activity, modification unit; as aforesaid compound (c); the preferred hydroxyl that uses the cyclic formal that contains hydroxyl is by acylations or silylanizing and protected compound, and more preferably the hydroxyl of glycerol formal is by acylations or silylanizing and protected compound.As its concrete example, can enumerate glycerol formal acetic ester etc.
Among the present invention, as the hydroxyl of above-mentioned polymerizable compound with hydroxyl by acylations or silylanizing and the usage quantity of protected compound (c), when considering the thermotolerance etc. of gained modified polyacetal resin, with respect to three 100 moles of ratios that are preferably 0.01 ~ 20 mole of alkane are especially preferably with respect to three
Figure 958715DEST_PATH_IMAGE001
Alkane is 0.1 ~ 10 mole for 100 moles.
In addition, when the preparation of modified polyacetal resin (A1), except mentioned component, usually also with the composition of regulating molecular weight, to regulate the molecular weight of resulting polymers.As the composition of regulating molecular weight, but illustration can not form unstable terminal chain-transfer agent, for example, as methylal, methoxy methyl acetal, dimethoxy methylal, trimethoxy methylal, oxygen methylene radical di-n-butyl ether, have the compound of alkoxyl group, can use it more than a kind or 2 kinds.Its usage quantity is preferably with respect to three
Figure 311199DEST_PATH_IMAGE001
Alkane 100 weight parts are 0.001 ~ 0.5 weight part.
Among the present invention, as the cationic polymerisation catalyst that uses when the preparation of modified polyacetal resin (A1), can enumerate plumbic chlorde, tin tetrachloride, titanium tetrachloride, aluminum chloride, zinc chloride, vanadium trichloride, butter of antimony, phosphorus pentafluoride, antimony pentafluoride, boron trifluoride, boron trifluoride diethyl etherificate thing, boron trifluoride dibutyl etherificate thing, boron trifluoride two
Figure 191430DEST_PATH_IMAGE001
Alkane salt; boron trifluoride acetic acid dehydration thing; boron trifluoride coordination compoundes such as boron trifluoride triethylamine complex compound; perchloric acid; the ethanoyl perchloric acid ester; tertiary butyl perchloric acid ester; oxyacetic acid; trichoroacetic acid(TCA); trifluoroacetic acid; inorganic and organic acid such as tosic acid; triethyl oxygen a tetrafluoro borate; the trityl group hexafluoro antimonate; allyl group diazonium hexafluorophosphate; complex chlorides such as allyl group diazonium a tetrafluoro borate; zinc ethyl; triethyl aluminum; metal alkylide salt such as diethyl aluminum muriate; heteropolyacid; more than a kind or 2 kinds of isopoly-acid etc.Wherein, particularly the mistake of polymerizability, reactivity and the catalyzer of modified polyacetal active aspect, the catalyzer of preferred Lewis acids system, preferred especially boron trifluoride, boron trifluoride diethyl etherificate thing, boron trifluoride dibutyl etherificate thing, boron trifluoride two Boron trifluoride coordination compoundes such as alkane salt, boron trifluoride acetic acid dehydration thing, boron trifluoride triethylamine complex compound.These cationic polymerisation catalysts can be direct, also can be with dilutions in advance such as organic solvent, and its preparation method is not particularly limited.
The amount of using as polymerizing catalyst, according to its kind and difference, but usually with respect to three
Figure 987665DEST_PATH_IMAGE001
Alkane is the scope of 1 ~ 1000ppm (weight basis), and preferred 1 ~ 500ppm, preferred especially 1 ~ 200ppm can suit selected by taking into account polymerization velocity or polymerization efficiency.
The inactivation that catalyzer after the polymerization causes because of neutralization is after polyreaction, adds basic cpd or its aqueous solution etc. and carries out to the formation reaction thing of being discharged by the polymerization machine or the resultant of reaction in the polymerization machine.The basic cpd of inactivation can use ammonia as being used for polymerizing catalyst is neutralized; Amines such as triethylamine, tributylamine, trolamine, three butanolamines; The hydroxide salts of basic metal, alkaline-earth metal; Other known catalyst deactivation agent.In addition, preferably after polyreaction, promptly add their aqueous solution, to carry out inactivation to resultant.
As mentioned above preparation, modified polyacetal resin (A1) with the side chain that has formed ester bond has preferably that 30 ~ 2000mmol/kg side chain forms ester group, the side chain that especially preferably has 50 ~ 500mmol/kg forms ester group.In addition, modified polyacetal resin (A1) so long as can melt-shaping then to its molecular weight or melt viscosity without any qualification, but preferred number average molecular weight is 1000 ~ 100000, melting index (MI) is about 0.01 ~ 200g/10min (according to ASTM D1238).
Described modified polyacetal resin (A1) can carry out terminal stabilization treatment by known method in the processing of following operation the time, also can not carry out terminal stabilization treatment and directly uses.
Then, method for hydrolysis preparation, modified polyacetal resin (A1) with the side chain that has formed ester bond is as mentioned above described.The present invention heat-treats the modified polyacetal resin (A1) of preparation as mentioned above in the presence of the hydrolysis treatment agent that is selected from quaternary ammonium compound and alkaline heterogeneous ring compound, with ester linkage hydrolyzing (saponification promptly) to form hydroxyl, and manufacturing has the modified polyacetal resin (A) of hydroxyl, it is characterized in that, by using described selective hydrolysis treatment agent to realize high percent hydrolysis, realization simultaneously has the stable manufacturing of the modified polyacetal resin (A) of hydroxyl.Hydrolysis is not limited by device especially, can use known device, and in addition, intermittent type, semibatch, continous way etc. appoint on the other hand that method all can adopt.
Hydrolysis with modified polyacetal resin (A1) of side chain formation ester group is the basis to heat-treat in the presence of the hydrolysis treatment agent that is selected from quaternary ammonium compound and alkaline heterogeneous ring compound, as long as then can be variety of way according to this basis, as preferred method for hydrolysis, the following 2 kinds of methods of illustration.
One (the 1st kind of method) is to make the modified polyacetal resin (A1) with ester group be dissolved in the medium method that is hydrolyzed under solution state.The heat treated temperature is preferably about 80 ~ 250 ℃, preferred especially 150 ℃ ~ 200 ℃.In addition, be preferably 5 fens heat-up time ~ 10 hours, preferred especially 20 minutes ~ 3 hours.The usage quantity of hydrolysis treatment agent forms ester group amount (mol) with respect to the side chain of modified polyacetal resin (A1) and is preferably 0.1 ~ 1000 equivalent, more preferably 2 ~ 200 equivalents, preferred especially 5 ~ 100 equivalents.
Be used to make the amount of modified polyacetal resin (A1) dissolved medium to be not particularly limited, but it is desirable to use about 0.1 ~ 50 liter with respect to modified polyacetal resin 100g.As being used to make modified polyacetal resin (A1) dissolved medium, so long as can modified polyacetal resin (A1) dissolved then be not particularly limited in above-mentioned heat treated temperature, the mixing solutions of water and alcohol, dimethyl formamide, dimethyl sulfoxide (DMSO) etc. easy to use and handle after separate also easy, so preferably.Heat treated is at normal pressure or add to depress and carry out.After the reason, by being cooled to normal temperature, solution makes modified polyacetal resin, afterwards, remove by the formaldehyde that filters, washing will be decomposed generation, unreacted monomer, oligopolymer, disaggregating treatment agent etc., by drying can be accomplished the modified polyacetal resin of high percent hydrolysis (A).
Another (the 2nd kind of method) is to make the modified polyacetal resin (A1) with ester group be scattered in the medium that does not dissolve modified polyacetal resin (A1) method that is hydrolyzed under slurry form.The heat treated temperature is preferably more than 80 ℃, the temperature of the fusing point of not enough modified polyacetal resin (A1), preferred especially 80 ~ 100 ℃.In addition, be preferably 1 ~ 50 hour heat-up time, preferred especially 2 ~ 10 hours.The usage quantity of hydrolysis treatment agent forms ester group amount (mol) with respect to the side chain of modified polyacetal resin (A1), is preferably 0.1 ~ 1000 equivalent, more preferably 5 ~ 500 equivalents, preferred especially 20 ~ 300 equivalents.
Be used to make the amount of modified polyacetal resin (A1) dispersive medium to be not particularly limited, but it is desirable to use about 0.1 ~ 100 liter with respect to modified polyacetal resin 100g.As being used to make modified polyacetal resin (A1) dispersive medium, so long as can under above-mentioned heat treated temperature, make modified polyacetal resin (A1) be separated into then being not particularly limited of slurry form, water, dimethyl formamide, dimethyl sulfoxide (DMSO) etc. are easy to use, and the separation after handling is also easy, so preferred.Like this, dimethyl formamide or dimethyl sulfoxide (DMSO) etc. as long as select the heat treated temperature, then also can be used as the medium use that is used for handling modified polyacetal resin (A1) under slurry form.Heat treated is at normal pressure or add to depress and carry out.After the processing, solution is cooled to normal temperature, afterwards, removes by the formaldehyde that filters, washing will be decomposed generation, unreacted monomer, oligopolymer, disaggregating treatment agent etc., by drying can be accomplished the modified polyacetal resin of high percent hydrolysis (A).
Among the present invention, can realize effective and stable hydrolysis by using the selective hydrolysis treatment agent, can be accomplished the modified polyacetal resin that contains hydroxyl (A) of the percent hydrolysis more than 70%, in the hydrolysis treatment under the solution state, also can be accomplished the modified polyacetal resin that contains hydroxyl (A) of the percent hydrolysis more than 90%.
In the modified polyacetal resin that contains hydroxyl (A) that obtains by hydrolysis treatment, can further cooperate known various stabilizer additive.As stablizer, can enumerate the wantonly more than a kind or 2 kinds of oxyhydroxide that hindered phenol based compound, trimeric cyanamide, guanamine, hydrazides, urea etc. contain nitrogen compound, alkali or alkaline-earth metal, inorganic salt, carboxylate salt etc.In addition,, can enumerate common additive, for example wantonly more than a kind or 2 kinds in tinting material such as dyestuff, pigment, lubricant, nucleator, releasing agent, antistatic agent, the tensio-active agent at thermoplastic resin as the additive that uses among the present invention.
Modified polyacetal resin that contains hydroxyl (A1) that gets by the present invention and composition thereof can also form by in extrusion molding, reaction-injection moulding, compression molding, vacuum forming, blow molding, the foaming and molding any.
Embodiment
Below, be described more specifically the present invention by embodiment, but the present invention is not limited by these embodiment.
[preparation] with modified polyacetal resin (A1 1) of the side chain that has formed ester bond
Three
Figure 460235DEST_PATH_IMAGE001
Alkane (moisture content 10ppm) 94mol% and 1, in the mixture of 3 dioxolane (moisture content 10ppm) 2mol%, glycerol formal acetic ester 4mol% (with respect to whole monomers), interpolation is as the methylal 50ppm (with respect to whole monomer weights) of molecular weight regulator, as the boron trifluoride (BF of reaction beginning catalyzer 3) 20ppm (with respect to whole monomer weights), carry out polymerization.By resulting polymers being imported in the aqueous solution contain 0.05 weight % triethylamine, further, separate, wash, drying and obtain having the modified polyacetal resin (A1 1) of ester in conjunction with side chain to carry out the inactivation of catalyzer.The import volume of ethanoyl in the polyacetal resin side chain is 200mmol/kg.
[preparation] with modified polyacetal resin (A1 2) of the side chain that has formed ester bond
Three
Figure 573684DEST_PATH_IMAGE001
In the mixture of alkane (moisture content 10ppm) 92mol% and glycerol formal acetic ester 8mol% (with respect to whole monomers), interpolation is as the methylal 50ppm (with respect to whole monomer weights) of molecular weight regulator, as the boron trifluoride (BF of reaction beginning catalyzer 3) 20ppm (with respect to whole monomer weights), carry out polymerization.By resulting polymers is imported contain 0.05 weight % triethylamine the aqueous solution to carry out the inactivation of catalyzer, further, separate, wash, drying and obtain having the modified polyacetal resin (A1 2) of ester in conjunction with side chain.The import volume of ethanoyl in the polyacetal resin side chain is 370mmol/kg.
[utilizing the manufacturing (dissolution method) of the modified polyacetal resin that contains hydroxyl of hydrolysis]
Embodiment 1 ~ 8, comparative example 1 ~ 2
In the modified polyacetal resin with the side chain that has formed ester bond (A1 1 or A1 2) 1g, add normal quaternary ammonium compound of regulation shown in the table 1 or alkaline heterogeneous ring compound (B 1 or B 2), with the aqueous solution 100ml of the mixture ratio of water/methyl alcohol=16:84, be heated to 170 ℃ and dissolve, under this temperature 2 hours, handle adding to depress.
After the processing, by solution is cooled to normal temperature, so that treated modified polyacetal resin is separated out, afterwards, remove by the formaldehyde that filters, washing will be decomposed generation, unreacted monomer, oligopolymer, disaggregating treatment agent etc., by carrying out drying, obtain the modified polyacetal resin that contains hydroxyl as purpose.
Percent hydrolysis (%) passes through 1H NMR is calculated by the peak (2.12ppm and 2.10ppm) of ethanoyl.The results are shown in table 1.
On the other hand, for not adding quaternary ammonium compound or alkaline heterogeneous ring compound in order to compare, the situation of using other basic cpd similarly to be hydrolyzed is shown in table 1 in the lump with the result.
The quaternary ammonium compound or the alkaline heterogeneous ring compound of＜use 〉
B 1: bursine
B 2:1,8 diazabicyclo [5.4.0] Shi one Tan Xi 7
The basic cpd that uses in＜the comparative example 〉
B 3: triethylamine
[table 1]
Figure 436598DEST_PATH_IMAGE002
。
[utilizing the manufacturing (slurry method) of the modified polyacetal resin that contains hydroxyl of hydrolysis]
Embodiment 9 ~ 11, comparative example 3 ~ 4
In the modified polyacetal resin with the side chain that has formed ester bond (A1 1 or A1 2) 1g, add normal quaternary ammonium compound of regulation shown in the table 1 or alkaline heterogeneous ring compound (B 1 or B 2) and water 20ml, by stir forming slurry form, under normal pressure, 100 ℃ of following heat treated 5 hours.
After the processing, solution is cooled to normal temperature, afterwards, removes, obtain the modified polyacetal resin that contains hydroxyl as purpose by carrying out drying by the formaldehyde that filters, washing will be decomposed generation, unreacted monomer, oligopolymer, disaggregating treatment agent etc.
Percent hydrolysis (%) passes through 1H NMR is calculated by the peak (2.12ppm and 2.10ppm) of ethanoyl.The results are shown in table 2.
On the other hand, the situation in order relatively not add quaternary ammonium compound or alkaline heterogeneous ring compound, to use other basic cpd similarly to be hydrolyzed is shown in table 2 in the lump with the result.
The quaternary ammonium compound or the alkaline heterogeneous ring compound of＜use 〉
B 1: bursine
B 2:1,8 diazabicyclo [5.4.0] Shi one Tan Xi 7
The basic cpd that uses in＜the comparative example 〉
B 4: sodium hydroxide
[table 2]
Figure 660906DEST_PATH_IMAGE003
。

Claims (11)

1.具有羟基的改性聚缩醛树脂(A)的制造方法，其特征在于，制备具有形成了酯键的侧链的改性聚缩醛树脂(A1)，在选自季铵化合物和碱性杂环化合物的水解处理剂的存在下对该改性聚缩醛树脂(A1)进行热处理，使酯键水解而形成羟基。 1. the manufacture method of the modified polyacetal resin (A) that has hydroxyl group, it is characterized in that, preparation has the modified polyacetal resin (A1) of the side chain that has formed ester bond, in being selected from quaternary ammonium compound and alkali The modified polyacetal resin (A1) is heat-treated in the presence of a hydrolysis treatment agent for a permanent heterocyclic compound to hydrolyze the ester bond to form a hydroxyl group. 2.权利要求1所述的改性聚缩醛树脂(A)的制造方法，其中，季铵化合物为下述通式(1)所示的化合物， 2. the manufacture method of modified polyacetal resin (A) described in claim 1, wherein, quaternary ammonium compound is the compound shown in following general formula (1), [R1R2R3R4N+]nXn − (1) [R 1 R 2 R 3 R 4 N + ] n X n − (1) 上述式中，R1、R2、R3、R4各自独立，表示碳原子数1~20的烃基，该烃基为直链或支链烷基、环烷基、芳基、芳烷基、或烷基芳基；烃基可具有取代基，取代基的种类为羟基、酰基、酰氧基、烷氧基、烷氧基羰基、羧基、氨基、酰胺基、乙烯基、烯丙基、羟基烷基氧基、烷氧基烷基氧基、和卤素原子；Xn −表示羟基、或来源于选自下述(i)~(ix)的化合物并与季铵形成盐的阴离子；n表示1以上的整数；n个[R1R2R3R4N+]可相互不同， In the above formula, R 1 , R 2 , R 3 , and R 4 are each independently representing a hydrocarbon group with 1 to 20 carbon atoms, and the hydrocarbon group is a straight-chain or branched-chain alkyl group, cycloalkyl group, aryl group, aralkyl group, Or alkylaryl; Hydrocarbyl can have substituents, the types of substituents are hydroxyl, acyl, acyloxy, alkoxy, alkoxycarbonyl, carboxyl, amino, amido, vinyl, allyl, hydroxyalkane Oxygen group, alkoxyalkyloxyl group, and halogen atom; Xn - represents hydroxyl group, or derives from the anion of the compound that is selected from following (i)～(ix) and forms salt with quaternary ammonium; n represents 1 The above integers; n [R 1 R 2 R 3 R 4 N + ] can be different from each other, (i)碳原子数1~20的羧酸、氢酸、含氧酸、无机硫代酸或碳原子数1~20的有机硫代酸 (i) Carboxylic acid, hydrogen acid, oxyacid, inorganic thioacid with 1 to 20 carbon atoms or organic thioacid with 1 to 20 carbon atoms (ii)酸性环状酰胺化合物 (ii) Acidic cyclic amides (iii)聚羧酸 (iii) polycarboxylic acid (iv)氨基羧酸 (iv) Amino carboxylic acid (v)碳酸单酯和/或碳酸氢金属盐 (v) Monocarbonate and/or Metal Bicarbonate (vi)酸性烯醇系化合物 (vi) Acidic enol compounds (vii)苯酚系化合物和/或醇系化合物 (vii) Phenolic compounds and/or alcohol compounds (viii)酸性吡咯化合物 (viii) Acidic pyrrole compounds (ix)选自有机硫化合物、有机磷化合物和有机硼化合物的非羧酸系化合物。 (ix) A non-carboxylic acid-based compound selected from organosulfur compounds, organophosphorus compounds, and organoboron compounds. 3.权利要求1所述的改性聚缩醛树脂(A)的制造方法，其中，碱性杂环化合物为1,8‐二氮杂双环[5.4.0]十一碳烯‐7或1,5‐二氮杂双环[4.3.0]壬烯‐5。 3. the manufacture method of modified polyacetal resin (A) described in claim 1, wherein, basic heterocyclic compound is 1,8-diazabicyclo[5.4.0]undecene-7 or 1 ,5‐diazabicyclo[4.3.0]nonene‐5. 4.权利要求1~3中任一项所述的改性聚缩醛树脂(A)的制造方法，其中，具有形成了酯键的侧链的改性聚缩醛树脂(A1)是通过将三
Figure 939567DEST_PATH_IMAGE001
烷(a)、选自不具有羟基的环状醚和环状甲缩醛的化合物(b)以及具有羟基的聚合性化合物的羟基通过酰基化或甲硅烷基化而被保护的化合物(c)，以(a)/(b)/(c)=100/0~30/0.01~20(摩尔比)的比例进行共聚而得的。 4. the manufacture method of the modified polyacetal resin (A) described in any one in claim 1～3, wherein, the modified polyacetal resin (A1) that has formed the side chain of ester bond is by making three
Figure 939567DEST_PATH_IMAGE001
Alkane (a), a compound (b) selected from cyclic ethers and cyclic formals without a hydroxyl group, and a compound (c) in which a hydroxyl group of a polymerizable compound having a hydroxyl group is protected by acylation or silylation , obtained by copolymerization at the ratio of (a)/(b)/(c)=100/0~30/0.01~20 (molar ratio). 5.权利要求4所述的改性聚缩醛树脂(A)的制造方法，其中，具有羟基的聚合性化合物选自含有羟基的环状甲缩醛、含有羟基的缩水甘油醚、含有羟基的氧杂环丁烷、含有羟基的苯乙烯以及含有羟基的乙烯基化合物。 5. The method for producing a modified polyacetal resin (A) according to claim 4, wherein the polymerizable compound having a hydroxyl group is selected from the group consisting of hydroxyl-containing cyclic formals, hydroxyl-containing glycidyl ethers, hydroxyl-containing Oxetanes, hydroxyl-containing styrenes, and hydroxyl-containing vinyl compounds. 6.权利要求5所述的改性聚缩醛树脂(A)的制造方法，其中，含有羟基的环状甲缩醛为环亚甲基甘油醚。 6. The method for producing a modified polyacetal resin (A) according to claim 5, wherein the hydroxyl-containing cyclic formal is cyclomethylene glyceryl ether. 7.权利要求1~6中任一项所述的改性聚缩醛树脂(A)的制造方法，其中，改性聚缩醛树脂(A1)具有30~2000mmol/kg的侧链形成酯基。 7. the manufacture method of the modified polyacetal resin (A) described in any one in claim 1～6, wherein, modified polyacetal resin (A1) has the side chain of 30～2000mmol/kg to form ester group . 8.权利要求1~7中任一项所述的改性聚缩醛树脂(A)的制造方法，其中，相对于改性聚缩醛树脂(A1)的侧链形成酯基量(mol)，使用0.1~1000当量的水解处理剂进行处理。 8. the manufacture method of the modified polyacetal resin (A) described in any one in claim 1～7, wherein, form ester group amount (mol) with respect to the side chain of modified polyacetal resin (A1) , use 0.1~1000 equivalent of hydrolysis treatment agent for treatment. 9.权利要求1所述的改性聚缩醛树脂(A)的制造方法，其特征在于，在能够溶解改性聚缩醛树脂(A1)的介质中使该改性聚缩醛树脂(A1)溶解，在水解处理剂的存在下，于80℃~250℃的温度下进行热处理。 9. the manufacture method of modified polyacetal resin (A) described in claim 1 is characterized in that, in the medium that can dissolve modified polyacetal resin (A1), make this modified polyacetal resin (A1) ) is dissolved, and heat-treated at a temperature of 80°C to 250°C in the presence of a hydrolysis treatment agent. 10.权利要求1所述的改性聚缩醛树脂(A)的制造方法，其特征在于，在不溶解改性聚缩醛树脂(A1)的介质中使该改性聚缩醛树脂(A1)分散，在水解处理剂的存在下，于80℃以上、不足该改性聚缩醛树脂(A1)的熔点的温度下，在改性聚缩醛树脂(A1)为浆料的状态下进行热处理。 10. the manufacture method of modified polyacetal resin (A) described in claim 1 is characterized in that, in the medium that does not dissolve modified polyacetal resin (A1), make this modified polyacetal resin (A1 ) dispersion, in the presence of a hydrolysis treatment agent, at a temperature of 80° C. or higher but lower than the melting point of the modified polyacetal resin (A1), in a state where the modified polyacetal resin (A1) is a slurry heat treatment. 11.权利要求1~10中任一项所述的改性聚缩醛树脂(A)的制造方法，其中，酯键的水解率为70%以上。 11. The manufacturing method of the modified polyacetal resin (A) in any one of Claims 1-10 whose hydrolysis rate of an ester bond is 70% or more.
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