CN105599169A - Method of manufacturing polyacetal guanules - Google Patents

Method of manufacturing polyacetal guanules Download PDF

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Publication number
CN105599169A
CN105599169A CN201510779519.9A CN201510779519A CN105599169A CN 105599169 A CN105599169 A CN 105599169A CN 201510779519 A CN201510779519 A CN 201510779519A CN 105599169 A CN105599169 A CN 105599169A
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particle
polyacetals
acid
foreign matter
manufacture method
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CN105599169B (en
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近藤知宏
木下阳介
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Asahi Kasei Corp
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Asahi Kasei Chemicals Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/16—Auxiliary treatment of granules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals

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  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Sorting Of Articles (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention relates to a method of manufacturing polyacetal guanules. The method can manufacture polyacetal guanules with less foreign matter and high purity. The method includes the steps: a granulation step: preparing polyacetal guanules less than 10 mass ppm which generates formaldehyde generated by the heating of 100 DEG C of the polyacetal by polymerization; and a screening step: screening the polyacetal guanules through a granule sorting machine so as to obtain polyacetal guanules containing foreign matter less than 600 mass ppm relative to the amount of the whole polyacetal guanules.

Description

The manufacture method of polyacetals particle
Technical field
The present invention relates to the manufacture method of polyacetals particle.
Background technology
Processability and the productivity ratio of polyacetals are good, therefore have can pass through melt injection molding,Melt extrude the forming methods such as moulding and effectively produce the excellent of the goods of desirable shape, partsPoint. Utilize such advantage, polyacetals be widely used in electric and electronic Material Field, automotive field,Other various industrial materials field, packaging for foodstuff field, parts Material Field. For thesePurposes, high and have the considerations such as thin molded article from appearance design, expect coloured differentThe polyacetals that thing is few, purity is high.
In order to reduce the foreign matter utilizing after the moulding that adds hot-working etc., consider to reduce polyacetals as far as possibleThe methods such as composition in addition, but for heat endurance, mechanical strength, mechanical strength stabilisation etc.,Must add the additive of the reason that may become foreign matter. Therefore, proposed by design to poly-The composition of the additive adding in acetal and suppress the technology of the generation of foreign matter.
For example, can enumerate: be combined with antioxidant and the oxide or the carbonate that are selected from magnesium or calciumIn more than one metallic compound, the polyacetals of PAG (for example, quoteDocument 1); Comprise polyacetals and select and freely gather (N-vinyl carboxylic acid acid amides) and N-vinyl carboxylicAt least a kind and choosing freedom in the group of the copolymer composition of acid acid amides and other vinyl monomerThe ester of PAG and its derivative, fatty acid amide, alcohols and aliphatic acid, alcohols andThe polyacetals (for example, patent documentation 2) of at least one in the group of the ester composition of dicarboxylic acids.
In addition, as the method for removing the foreign matter in polymer, can enumerate in order to utilize hot-fluidWhen the injection moulding in road, suppress metallic foreign body and stop up hot flow path, with magnetic grader sorting for notePenetrate the particle (only take out metal and sneak into few particle) of moulding technology (for example, patent documentation 3),From resin particle, remove the technology (for example, patent documentation 4) of colored particles.
Prior art document
Patent documentation
Patent documentation 1: Japanese kokai publication hei 7-228751 communique
Patent documentation 2: TOHKEMY 2001-247745 communique
Patent documentation 3: TOHKEMY 2004-99682 communique
Patent documentation 4: Japanese kokai publication hei 2-253891 communique
Summary of the invention
Invent problem to be solved
But, for disclosed polyacetals in above-mentioned patent documentation 1,2, not about treeThe record of the impact of the control of fat viscosity, the variation of manufacture etc. In addition, above-mentioned patent documentation 3Technology specifically make resin particle by the technology of magnetic grader, can not fully removeThe metal that granule interior comprises, once in addition owing to being conducted oneself with dignity and it by the particle utilization of magnet adsorptionThereby falling, the collision of the particle passing through afterwards the reason such as can not remove completely, the removing of foreign matter (metal)Go insufficient. The technology of patent documentation 4 has been recorded the method for removing of the foreign matter in particle, but does not haveHave the state of its optimum particle is recorded, also do not mention in addition polyacetals particle.
Therefore, the object of the present invention is to provide the highly purified polyacetals that can manufacture few foreignThe manufacture method of the polyacetals particle of particle. It is a kind of poly-that object of the present invention is further to provideThe manufacture method of acetal, the generation of black foreign matter when it can suppress melt-processed effectively,Can effectively manufacture highly purified polyacetals.
For the means of dealing with problems
The inventor etc. conduct in-depth research in order to solve the problem of above-mentioned prior art, knotFruit finds to have the manufacture method of specific granulating working procedure and specific sorting operation by utilizationManufacture polyacetals particle, can obtain the highly purified polyacetals particle of few foreign, thereby completeThe present invention.
, the present invention is as described below.
[1] manufacture method for polyacetals particle, it comprises following operation:
Granulating working procedure, obtain heating by 100 DEG C by the polyacetals obtaining by polymerization andThe amount of the formaldehyde producing is the polyacetals particle below 10 quality ppm; With
Sorting operation, carries out sorting by particle-size distributor to above-mentioned polyacetals particle, therebyAmount to the polyacetals particle that contains foreign matter with respect to the amount of whole polyacetals particles is less than 600 matterThe polyacetals particle of amount ppm.
[2], according to the manufacture method of the polyacetals particle [1] described, wherein, above-mentioned foreign matter is sourceIn the foreign matter of carbide.
[3] according to the manufacture method of the polyacetals particle [1] or [2] described, wherein, above-mentioned polyacetalsParticle be shaped as oblate spheroid.
[4] according to the manufacture method of the polyacetals particle described in any one in [1]～[3], wherein, onThe longest diameter of stating polyacetals particle is that 5mm is following, the shortest diameter is below 3mm.
[5] according to the manufacture method of the polyacetals particle described in any one in [1]～[4], wherein, onState foreign matter and be less than 1.0mm.
[6] according to the manufacture method of the polyacetals particle described in any one in [1]～[5], wherein, onState sorting operation and be the whole of the polyacetals particle that utilizes above-mentioned particle-size distributor to remove or oneDivide the sorting operation as the polyacetals recycling of above-mentioned granulating working procedure.
[7] according to the manufacture method of the polyacetals particle described in any one in [1]～[6], wherein, onState foreign matter and be less than 0.3mm,
Above-mentioned sorting operation is to obtain with respect to the above-mentioned bunching that contains foreign matter of polyacetals particle total amountThe amount of aldehyde particle is the sorting operation of the polyacetals particle below 300 quality ppm.
[8] according to the manufacture method of the polyacetals particle described in any one in [1]～[7], wherein, onStating granulating working procedure and be the amount that obtains the formaldehyde producing by the heating of 120 DEG C is 10 quality ppmThe granulating working procedure of the polyacetals particle of following polyacetals.
Invention effect
According to the manufacture method of polyacetals particle of the present invention, can manufacture the high-purity of few foreignPolyacetals particle.
Detailed description of the invention
Below, to detailed for implementing mode of the present invention (following, to be called " present embodiment ")Ground explanation. Following present embodiment is for illustration of the present invention being described, the invention is not restricted toFollowing content. The present invention can carry out implementing after various distortion in the scope of its main idea.
The manufacture method of the polyacetals particle of present embodiment comprises following operation:
Granulating working procedure, obtain heating by 100 DEG C by the polyacetals obtaining by polymerization andThe amount of the formaldehyde producing is the polyacetals particle below 10 quality ppm; With
Sorting operation, carries out sorting by particle-size distributor to above-mentioned polyacetals particle, therebyAmount to the polyacetals particle that contains foreign matter with respect to the total amount of polyacetals particle is less than 600 qualityThe polyacetals particle of ppm.
<polyacetals>
Polyacetals in present embodiment can be enumerated: by formaldehyde, metaformaldehyde or four polyformaldehydeDeng the homopolymerization of cyclic oligomer and obtain in fact by Oxymethylene unit-(CH2O)-formPolyoxymethylene homopolymers or by formaldehyde and/or metaformaldehyde, with cyclic ether and/or ring-type contractingFormaldehyde, be added with the above and following hindered phenol anti-oxidants of 500 quality ppm of 1 quality ppmCyclic formals copolymerization and having of obtaining comprising Oxymethylene unit-(CH2O)-chainIn be randomly inserted with the polyoxy methylene of the structure of the represented oxygen alkylidene unit of following general formula (1)Base co-polymer etc.
(the R in formula1And R2Respectively do for oneself hydrogen atom, alkyl or aryl, they can identically also canWith difference, the integer that n is 2～6)
In the polyoxymethylene copolymer using in present embodiment, also comprise strand collateralizationAfter side chain polyoxymethylene copolymer and with the Oxymethylene weight containing more than 50 quality %The polyoxymethylene block copolymer of the variety classes composition block of multiple unit.
In addition, the insertion rate of the above-mentioned oxygen alkylidene unit in polyoxymethylene copolymer with respect to100 moles of Oxymethylene unit preferably 0.01 mole above and below 50 moles, more preferably0.03 mole of above and 20 moles of following scope. As this oxygen alkylidene unit, for example, can liftGo out oxygen ethylidene unit, oxygen propylidene unit, oxygen tetramethylene unit, oxygen butylidene unit,Oxygen phenyl ethylidene unit etc. In these oxygen alkylidene units, from making polyacetal resin compositePhysical property raising aspect consider, preferably oxygen ethylidene unit-[(CH2)2O]-and oxygen tetramethylene unit-[(CH2)4O]-。
The polyacetals obtaining by above-mentioned homopolymerization or copolymerization preferably carries out the stabilisation of molecular endProcess. As the stabilization treatment method of molecular end, can use for example by the hydroxyl of endMethods such as esterification, etherificate, urethane or the l fraction of molecular end is passed throughHydrolysis and the method for stabilisation etc.
For example, can pass through: will be by formaldehyde and/or metaformaldehyde and cyclic ether and/or ring-type contractingThe copolymerization of formaldehyde and the polyoxymethylene copolymer that obtains carries out immediately molecular end after polymerizationThe operation of stabilization processes, afterwards under molten condition continuously for to can implement injected water orAlcohol or their mixture mixing operation and by hydroxyl chemical combination such as the above-mentioned water injectingThe different directions of the devolatilization operation that the steam of thing and free formaldehyde discharge rotates non-occlusal patternDouble screw extruder is also processed etc. and obtains such polyacetals. In addition, above-mentioned in injectionWater or alcohol or their mixture when mixing, preferably add the alkaline matters such as triethylamine and doFor pH adjusting agent.
In the polyacetals of present embodiment, in the scope of effect of not damaging present embodiment,Can be used alone or in combination the additive using in polyacetals in the past, for example heat stabilizer,Weather-proof (light) stabilizing agent, releasing agent etc.
As heat stabilizer, can enumerate the agent for capturing of antioxidant, formaldehyde or formic acid or theyAnd use, preferred anti-oxidant and agent for capturing are also used.
As antioxidant, preferably hindered phenol anti-oxidants, for example can enumerate 3-(3 ', 5 '-bis-unclesButyl-4 '-hydroxy phenyl) propionic acid n-octadecane base ester, 3-(the 3 '-methyl-5-tert-butyl group-4 '-hydroxy phenyl)Propionic acid n-octadecane base ester, 3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid n-tetradecane base ester,1,6-hexylene glycol two (3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester), BDO pairTwo (3-(the 3-tert-butyl group-5-the methyl of (3-(3,5-di-tert-butyl-hydroxy phenyl)-propionic ester), triethylene glycol-4-hydroxy phenyl) propionic ester), four (methylene-3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic estersMethane, 3,9-two (2-(3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionyloxy)-1,1-dimethylEthyl)-2,4,8,10-tetra-oxaspiros (5.5) hendecane, N, N '-bis--3-(3 ', 5 '-di-t-butyl-4-hydroxylPhenol) propiono hexamethylene diamine, N, N '-tetramethylene is two-3-(3 '-methyl-5 '-tert-butyl group-4-Hydroxyl phenol) propiono diamines, N, N '-bis--(3-(3,5-di-t-butyl-4-hydroxyl phenol) propiono)Hydrazine, N-salicyl-N '-salicylidene base hydrazine, 3-(N-salicyl) amino-1,2,4-triazole, N, N '-Two (2-(3-(3,5-dibutyl-4-hydroxy phenyl) propionyloxy) ethyl) hydroxy amide etc.
In these hindered phenol anti-oxidants, the preferably two (3-(3 tert-butyl groups-5-methyl-4-of triethylene glycolHydroxy phenyl)-propionic ester), four (methylene-3-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic ester firstAlkane.
As the agent for capturing of formaldehyde, formic acid, particularly, can enumerate (a) and contain formolite reactionThe hydroxide of nitrogen compound and polymer, (b) alkali metal or alkaline-earth metal, inorganic acid salt,Carboxylate and alkoxide etc.
Contain formolite reaction nitrogen compound as (a), particularly, can enumerate (1) dicyandiamide,(2) amino triazine, (3) amino cocondensation compound that replaces triazine and formaldehyde etc. of replacing. As (2) aminoReplace triazine, particularly, have guanamines (2,4-diaminourea s-triazine), melamine (2,4,6-tri-Amino s-triazine), N-melamine-butyl, N phenyl melamine, N, N-diphenyl melamineAmine, N, N-diallyl melamine, N, N ', N " triphenyl melamine, N-methylol trimerizationCyanamide, N, N '-dihydroxymethyl melamine, N, N ', N " trimethylol melamine, benzoguanamine (2,4-Diaminourea-6-phenyl s-triazine), 2,4-diaminourea-6-methyl s-triazine, 2,4-diaminourea-6-butylS-triazine, 2,4-diaminourea-6-benzyloxy s-triazine, 2,4-diaminourea-6-butoxy s-triazine, 2,4-Diaminourea-6-cyclohexyl s-triazine, 2,4-diaminourea-6-chloro-s-triazine, 2,4-diaminourea-6-sulfydryl is equalTriazine, 2, the amino s-triazine of 4-dihydroxy-6-(ア メ ラ イ ト), 2-hydroxyl-4,6-diaminourea s-triazine (アメ リ Application), N, N, N ', N '-four cyano ethylo benzene guanamines etc. As (3) amino triazine and the formaldehyde of replacingCocondensation compound, particularly, have melamine-formaldehyde condensation products etc. Among them, preferablyDicyandiamide, melamine and melamine-formaldehyde condensation products.
There is the polymer of formolite reaction nitrogen base as (a), particularly, can enumerate (1) polyamidesPolyimide resin, (2) are by acrylamide and its derivative or acrylamide and its derivative and other etheneBase monomer under the existence of metal alkoxide polymerization and the polymer that obtains, (3) by acrylamide and itsDerivative or acrylamide and its derivative and other vinyl monomer are in the existence of radical polymerizationLower polymerization and polymer, (4) amine, acid amides, urea and the carbamate etc. that obtain contain nitrogen basePolymer etc. As the polyamide of (1), particularly, can enumerate nylon 4-6, nylon 6,Nylon 6-6, nylon 6-10, nylon 6-12, nylon 12 etc. and their copolymer nylon 6/6-6,Nylon 6/6-6/6-10, nylon 6/6-12 etc. As (2) acrylamide and its derivative or acryloylAmine and its derivative and other vinyl monomer polymerization and gathering of obtaining under the existence of metal alkoxideCompound, particularly, can enumerate poly--Beta-alanine copolymer etc. Can pass through Japanese Patent PublicationNo. 6-12259, No. 5-87096, Japanese Patent Publication, No. 5-47568, Japanese Patent Publication and Japan are specialOpen the method for each communique record of flat No. 3-234729 and manufacture these polymer. Can be by JapanThe method manufacture (3) that Unexamined Patent 3-28260 communique is recorded is by acrylamide and its derivative or thirdThe polymerization and obtaining under the existence of radical polymerization of alkene acid amides and its derivative and other vinyl monomerThe polymer arriving.
As hydroxide, inorganic acid salt, carboxylate and the alkoxide of (b) alkali metal or alkaline-earth metal,Particularly, can enumerate the hydroxide of sodium, potassium, magnesium, calcium or barium etc., the carbonic acid of this metalSalt, phosphate, silicate, borate, carboxylate. The carboxylic acid of this carboxylate for having 10～Saturated or the unsaturated aliphatic carboxylic acids of 36 carbon atoms etc., these carboxylic acids can be replaced by hydroxyl.As representative examples of saturated aliphatic carboxylic, can enumerate capric acid, laurate, myristic acid, palmitic acid, hardResin acid, arachidic acid, behenic acid, tetracosanoic acid, cerinic acid, montanic acid, melissic acid, 36Acid. Unsaturated aliphatic carboxylic acid can be enumerated undecenoic acid, oleic acid, elaidic acid, 22 carbonOlefin(e) acid, erucic acid, brassidic acid, sorbic acid, linoleic acid, leukotrienes, arachidonic acid, thirdAcetylenic acid, stearolic acid etc. In addition, as alkoxide, can enumerate methoxide, the second of above-mentioned metalAlkoxide etc.
As weather-proof (light) stabilizing agent, preferably (a) benzotriazole material, (b) oxanilide class thingMatter and (c) hindered amines material.
As (a) benzotriazole material, particularly, can enumerate 2-(2 '-hydroxyl-5 '-methyl-benzeneBase) BTA, 2-[2 '-hydroxyl-3,5-di-t-butyl-phenyl) BTA, 2-[2 '-hydroxyl-3,5-Diisoamyl-phenyl] BTA, 2-[2 '-hydroxyl-3,5-is two-(alpha, alpha-dimethylbenzyl) phenyl]-2H-BTA, 2-(2 '-hydroxyl-4 '-octyloxyphenyl) BTA etc., be preferably 2-[2 '-hydroxyl-3,5-is two-(alpha, alpha-dimethylbenzyl) phenyl] and-2H-BTA, 2-[2 '-hydroxyl-3,5-di-t-butyl-benzeneBase) BTA.
As (b) oxanilide class material, particularly, can enumerate 2-ethyoxyl-2 '-ethyl oxalylDiphenylamines, the 2-ethyoxyl-5-tert-butyl group-2 '-ethyl oxalyl diphenylamines, 2-ethyoxyl-3 '-dodecylOxalyl diphenylamines etc. These materials can use separately separately, also can be used in combination 2 kinds withOn.
As (c) hindered amines material, particularly, can enumerate 4-acetoxyl group-2,2,6,6-tetramethylPhenylpiperidines, 4-stearoyl-oxy-2,2,6,6-tetramethyl piperidine, 4-acryloxy-2,2,6,6-tetramethylPhenylpiperidines, 4-(phenylacetyl oxygen base)-2,2,6,6-tetramethyl piperidine, 4-benzoyloxy-2,2,6,6-Tetramethyl piperidine, 4-methoxyl group-2,2,6,6-tetramethyl piperidine, the stearic oxygen of 4-base-2,2,6,6-tetramethylPiperidines, 4-cyclohexyloxy-2,2,6,6-tetramethyl piperidine, 4-benzyloxy-2,2,6,6-tetramethyl piperidine,4-phenoxy group-2,2,6,6-tetramethyl piperidine, 4-(ethylamino formyloxy)-2,2,6,6-tetramethyl piperazinePyridine, 4-(cyclohexyl carboxyamide oxygen base)-2,2,6,6-tetramethyl piperidine, 4-(phenyl amino methanoylBase)-2,2,6,6-tetramethyl piperidine, carbonic acid two (2,2,6,6-tetramethyl-4-piperidines) ester, oxalic acid two(2,2,6,6-tetramethyl-4-piperidyl) ester, malonic acid two (2,2,6,6-tetramethyl-4-piperidyl) ester,Decanedioic acid two (2,2,6,6-tetramethyl-4-piperidyl) ester, adipic acid two (2,2,6,6-tetramethyl-4-piperidinesBase) (ester), terephthalic acid (TPA) two (2,2,6,6-tetramethyl-4-piperidyl) ester, 1, two (2,2,6, the 6-tetra-of 2-Methyl-4-piperidyl oxygen base)-ethane, α, α '-bis-(2,2,6,6-tetramethyl-4-piperidyl oxygen base)-to twoToluene, Toluene-2,4-diisocyanate, 4-diamino acid two (2,2,6,6-tetramethyl-4-piperidyl) ester, hexa-methylene-1,6-diamino acid two (2,2,6,6-tetramethyl-4-piperidyl) ester, benzene-1,3,5-tricarboxylic acid three(2,2,6,6-tetramethyl-4-piperidyl) ester, benzene-1,3,4-tricarboxylic acid three (2,2,6,6-tetramethyl-4-piperidinesBase) ester etc., be preferably decanedioic acid two (2,2,6,6-tetramethyl-4-piperidyl)-ester. Above-mentioned hindered aminesMaterial can use separately separately, also can be used in combination two or more. In addition, more preferably go upState the combination of benzotriazole material, oxanilide class material and hindered amines material.
As releasing agent, can enumerate ester, alcohol and the dicarboxylic acids of alcohol and alcohol and aliphatic acidEster, silicone oil etc.
As alcohol, particularly, there are monohydric alcohol, polyalcohol, for example, as the example of monohydric alcohol,Can enumerate octanol, n-octyl alcohol (カ プ リ Le ア Le コ mono-Le), nonyl alcohol, decyl alcohol, tip-nip, the moonCinnamic alcohol, tridecanol, myristyl alcohol, pentadecanol, cetanol, heptadecanol, stearyl alcohol,Oleyl alcohol, nonadecanol, eicosanol, docosyl alcohol, ceryl alcohol, melissyl alcohol, 2-hexyl decyl alcohol, 2-Octyldodecanol, 2-decyl tetradecanol, synthctic fat family alcohol (ユ ニ リ ソ ア Le コ mono-Le) etc.As polyalcohol, for containing the polyalcohol of 2～6 carbon atoms, for example, can enumerate ethylene glycol, twoEthylene glycol, triethylene glycol, propane diols, DPG, butanediol, pentanediol, hexylene glycol,Glycerine, two glycerine, triglycerin, threitol, erythrite, pentaerythrite, arabitol, riboseAlcohol, xylitol, sorbierite, anhydrosorbitol, D-sorbite, sweet mellow wine etc.
As the ester of alcohol and aliphatic acid, in fatty acid cpds, preferably by being selected from palmitic acid, hardAliphatic acid in resin acid, behenic acid, montanic acid be selected from glycerine, pentaerythrite, dehydration sorbThe fatty acid ester of the polyol derivative in sugar alcohol, D-sorbite. These fatty acid ester compounds canThere is hydroxyl, also can not there is not hydroxyl, fatty acid ester compound is not limited. For example,Can be that monoesters can be also diester, three esters. In addition, can be with boric acid etc. by hydroxy-end capped.
As preferred fatty acid ester, particularly, can enumerate glycerine monopalmitate, glycerineDipalmitate, tripalmitin, glyceryl monostearate, glycerol distearate,Glycerol tristearate, Glyceryl monobehenate, glycerine two behenates, glycerine three behenic acidsEster, glycerine list montanate, glycerine two montanates, glycerine three montanates, pentaerythriteMonopalmitate, pentaerythrite dipalmitate, pentaerythrite tripalmitate, pentaerythriteFour palmitates, pentaerythritol monostearate, pentaerythritol stearic acid ester 2, pentaerythriteTristearate, pentaerythritol tetrastearate, pentaerythrite list behenate, pentaerythriteTwo behenates, pentaerythrite three behenates, pentaerythrite four behenates, pentaerythriteSingle montanate, pentaerythrite two montanates, pentaerythrite three montanates, pentaerythriteFour montanates, sorbitan-monopalmityl ester, anhydrosorbitol dipalmitate,Anhydrosorbitol tripalmitate, anhydrosorbitol monostearate, anhydrosorbitolDistearate, anhydrosorbitol tristearate, anhydrosorbitol list behenate,Anhydrosorbitol two behenates, anhydrosorbitol three behenates, anhydrosorbitolSingle montanate, anhydrosorbitol two montanates, anhydrosorbitol three montanates,D-sorbite monopalmitate, D-sorbite dipalmitate, D-sorbite tripalmitate,D-sorbite monostearate, D-sorbite distearate, D-sorbite tristearate,D-sorbite list behenate, D-sorbite two behenates, D-sorbite three behenates,D-sorbite list montanate, D-sorbite two montanates, D-sorbite three montanates etc.
In addition, as with boric acid etc. by the aliphatic ester compound after hydroxy-end capped, also can enumerateThe borate of fatty acid monoglyceride. With regard to the ester of alcohol and dicarboxylic acids, can enumerate as alcoholMethyl alcohol, ethanol, propyl alcohol, n-butanol, isobutanol, the tert-butyl alcohol, n-amyl alcohol, 2-amylalcohol, justEnanthol, n-octyl alcohol, n-nonyl alcohol, laruyl alcohol, myristyl alcohol, cetanol, stearyl alcohol, mountain YuAlcohol etc. are saturated/unsaturated alcohol and oxalic acid as dicarboxylic acids, malonic acid, butanedioic acid, glutaric acid,Adipic acid, pimelic acid, suberic acid, azelaic acid, decanedioic acid, heneicosanedioic acid, tridecane twoMonoesters, the diester etc. of acid, maleic acid, fumaric acid, glutaconate etc.
[manufacture method of polyacetals]
As the manufacture method of the polyacetals of present embodiment, can use the list with steam ventThe extruder of screw rod or twin-screw carries out melting mixing and manufactures. As mentioned above, polyacetals is for poly-Oxymethylene homopolymers, polyoxymethylene copolymer etc.
[manufacture method of polyacetals: polyoxymethylene homopolymers]
Polyoxymethylene homopolymers is for low by ring-types such as formaldehyde or metaformaldehyde, four polyformaldehydeThe homopolymerization of polymers and obtain in fact by Oxymethylene unit-(CH2The polyoxy methylene of O)-formationBase, for two ends of polymer chain are by the homopolymers after ester group or ether end-blocking. For exampleCan, using formaldehyde and known molecular weight regulator as raw material, use knownGathering of saltClose catalyst, using hydrocarbon etc. as solvent, by known slurry method, for example Japanese Patent PublicationThe polymerization of recording in 47-6420 communique, Japanese Patent Publication 47-10059 communique etc. obtainsPolyoxymethylene homopolymers. Herein, formaldehyde does not preferably contain the impurity such as water, methyl alcohol.
As polymerization catalyst, as long as be just not particularly limited for anionic polymerization catalyst,Be for exampleSalt polymerization catalysts etc. particularly, are the represented material of following general formula (2).
[R3R4R5R6M]+×-···(2)
(in formula, R3、R4、R5、R6Represent independently of one another alkyl, M represents to have lonely to electricityThe element of son, X represents nucleophilic group. )
Above-mentioned general formula (2) is representedIn salt polymerization catalyst, preferably use tetraethyl iodateThe iodate of tributyl ethylIn seasonSalt compounds, 4 bromide, dimethyl twoThe quaternary ammonium compounds such as stearyl ammonium acetate. More preferably use dimethyl distearyl ammonium acetate.
The import volume of polymerization catalyst with respect to monomer 1kg be preferably 0.0001 mole above andBelow 0.01 mole, more preferably more than 0.0005 mole and below 0.005 mole, furtherMore than being preferably 0.001 mole and below 0.003 mole. Import volume is when more than 0.0001 mole,Polymerization speed accelerates, and yield improves, preferred at economic aspect. Import volume is below 0.01 moleTime, polymerization system easily becomes evenly, thereby preferably.
As molecular weight regulator, particularly, use alcohol, carboxylic acid anhydrides, carboxylic acid etc., preferablyFor methyl alcohol, ethanol, propionic andydride, acetic anhydride, more preferably acetic anhydride. Molecular weight regulatorImport volume with respect to monomer 1kg preferably 0.005 mole above and below 0.008 mole.
As hydrocarbon equal solvent, as long as for not just to be not particularly limited with the compound of formolite reaction,Be preferably pentane, isopentane, hexane, cyclohexane, heptane, octane, nonane, decane, benzeneDeng. More preferably hexane. In addition, also two or more can be mixed and uses.
Polyplant as long as can supply with simultaneously formaldehyde, molecular weight regulator,Salt Type of CollectiveThe device of catalyst is just not particularly limited, and can use known device, can be batch-type,Continous way etc. Be preferably the polyplant of continous way.
The terminal groups major part of the polyoxymethylene homopolymers obtaining is like this hydroxyl, and therefore heat is notStable, can make end stabilisation.
As by the method for end stabilisation, can enumerate known terminal groups is carried out to chemical treatmentMethod. For example, with respect to polymer 1kg, drop into 0.1kg above and chemical below 90kgInorganic agent, in temperature is more than 140 DEG C and below 150 DEG C, the time is more than 20 minutes and 100Minute carry out below chemical treatment. Device can be that continous way can be also batch-type, is preferablyContinous way device. In addition, chemical treatments can use the chemical treatment such as esterifying agent, etherifying agentAgent, the chemical treatments of the terminal groups in present embodiment is preferably esterifying agent.
Using in the method for esterifying agent as chemical treatments, can enumerate United States Patent (USP) theThe method that a large amount of acid anhydrides of use of recording in No. 3459709 descriptions carries out with slurry form andThe gas of the use acid anhydrides of recording in No. 3172736 description of United States Patent (USP) carries out with gas phaseMethod etc.
As esterifying agent, carry out with gas phase at the method for carrying out with slurry form, use gasIn any of method, can enumerate the represented organic acid anhydride of following general formula (3), benzoyl oxide,Succinyl oxide, maleic anhydride, glutaric anhydride, phthalic anhydride etc.
R7COOCOR8···(3)
(in formula, R7、R8Represent independently of one another alkyl. R7、R8Can be the same or different. )
In the represented organic acid anhydride of above-mentioned general formula (3), preferably propionic andydride, acetic anhydride, more excellentSelect acetic anhydride. Organic acid anhydride can use a kind also can use two or more.
As the method that uses etherifying agent as chemical treatments, there is Japanese Patent Publication No. 63-452The method of recording in communique etc., the etherifying agent using in the end stabilisation as present embodiment,Ortho esters be can enumerate, aliphatic or aromatic acid and aliphatic, alicyclic or fragrant conventionally can be enumeratedThe ortho esters of fragrant family alcohol etc., particularly, can enumerate original acid A ester or ethyl orthoformate, formerMethyl acetate or ethyl orthoacetate and former methyl benzoate or former ethyl benzoate, orthocarbonic ester,Ethyl orthocarbonate etc.
In etherification reaction, preferably and 0.02kg above with respect to etherifying agent 1kg importing 0.001kgIntensity organic acid, dimethyl suflfate, sulfuric acid in following p-methyl benzenesulfonic acid, acetic acid, hydrobromic acid etc.The catalyst of Louis's acid types such as the middle intensity inorganic acid such as diethylester.
The preferred solvent of etherification reaction be the low boiling aliphatic such as pentane, hexane, cyclohexane, benzene,Alicyclic and aromatic hydrocarbon; The halo lower aliphatic such as carrene, chloroform, carbon tetrachloride etc.Organic solvent.
The mode of polymerization is not particularly limited, in order easily to obtain polyoxymethylene homopolymersPowder, is preferably slurry polymerization, polymerisation in bulk.
[manufacture method of polyacetals: polyoxymethylene copolymer]
By formaldehyde and/or metaformaldehyde and cyclic ether and/or cyclic formals or be added with 1 matterThe cyclic formals of the hindered phenol anti-oxidants more than amount ppm and below 500 quality ppmCopolymerization and having of obtaining comprising Oxymethylene unit-(CH2O)-chain in be randomly inserted withThe material of the structure of the represented oxygen alkylidene unit of following general formula (1) is polyoxymethylene copolymerizationThing.
(the R in formula1And R2Respectively do for oneself hydrogen atom, alkyl or aryl, they can identically also canWith difference, the integer that n is 2～6)
Metaformaldehyde refers to the cyclic trimer of formaldehyde, for example, and by depositing at acidic catalystUnder make formlinata aquae concentratac reaction and obtain. In this metaformaldehyde, contain water, methyl alcohol,The impurity that formic acid, methyl formate etc. shift its chain, therefore preferably removes by methods such as distillationsThese impurity and purifying. Now, preferably with respect to 1 mole of impurity that chain is shifted of metaformaldehydeTotal amount be adjusted to 1 × 10-3Below mole, more preferably 0.5 × 10-3Below mole. 1 × 10-3Below mole time, polymerization rate can be not slack-off, the good thermal stability of the polymer of generation.
Cyclic ether and/or cyclic formals be can with the composition of metaformaldehyde copolymerization, concrete andSpeech, can enumerate oxirane, expoxy propane, epoxy butane, chloropropylene oxide, epibromohydrin, oxidationStyrene, oxetanes, 1,3-dioxolane, ethylene glycol acetal, propane diols contracting firstAldehyde, diethylene glycol formal, triethylene glycol formal, BDO formal, 1,5-penta 2Alcohol formal, 1,6-hexylene glycol formal etc. In these cyclic ethers and/or cyclic formals, preferably1,3-dioxolane, BDO formal.
The addition of cyclic ether and/or cyclic formals is preferably 1 with respect to 1 mole of metaformaldehyde% by mole above and below 20 % by mole, more preferably 1 % by mole above and below 15 % by mole,More preferably 1 % by mole above and below 10 % by mole, be particularly preferably 1 % by mole withUpper and below 5 % by mole.
As polymerization catalyst, the cations such as preferred Lewis acids, Bronsted acid and its ester or acid anhydride are livedProperty catalyst. As lewis acid, for example, can enumerate boron, tin, titanium, phosphorus, arsenic and antimonyHalide etc., particularly, can enumerate boron trifluoride, butter of tin, titanium tetrachloride, five fluorineChange phosphorus, phosphorus pentachloride, antimony pentafluoride and its complex compound or salt etc. In addition, as Bronsted acid,Its ester or acid anhydride, particularly, can enumerate perchloric acid, TFMS, heteropoly acid, isopolyacid,The perchloric acid tert-butyl ester, acetylperchlorate, trimethyl oxygenHexafluorophosphoric acid ester etc. Among them,Preferably boron trifluoride, boron trifluoride hydrate; The organic compound that contains oxygen atom or sulphur atomWith the co-ordination complex of boron trifluoride, particularly, can enumerate three as preferred example and fluoridizeBoron Anaesthetie Ether, boron trifluoride di-n-butyl ether. The use amount of these polymerization catalysts with respect to1 mole of the total amount of formaldehyde and/or metaformaldehyde and cyclic ether and/or cyclic formals is preferred1×10-6Mole above and 1 × 10-3Below mole, more preferably 5 × 10-6Mole above and 1 × 10-4Below mole.
From the viewpoint of what react equably, preferably with polymerisation not being caused to bad shadowThe above-mentioned catalyst using in the atent solvent dilution present embodiment of ringing also adds in monomer.The solvent of using as catalyst dilution, as long as the organic solvent that does not participate in polymerisation just all canTo use. For example, can use the aromatic hydrocarbon such as benzene,toluene,xylene; N-hexane, positive heptanThe aliphatic hydrocarbon such as alkane, cyclohexane; The halogenated hydrocarbons such as chloroform, carrene; Ether, diethylene glycol twoThe ethers such as methyl ether, Isosorbide-5-Nitrae-dioxane etc. These solvents are preferably adjusted to moisture specificScope, use after can fully removing moisture by zeolite etc.
As the polymerization of polyoxymethylene copolymer, can adopt slurry method, substance law,In fusion method etc. any. In addition, the shape (structure) of the polymerisation machine of use is not special yetRestriction, the oar formula of the twin-screw that preferably thermal medium can circulate in chuck, the stirring of screwMixed type polyplant. As the polyplant that carries out using in the bulk polymerization of continous way,Can use common kneader, the continuous extruder and mixing roll of double-screw type, twin-screw oar type to mix continuouslyThe self-cleaning types such as machine are extruded the continuous polymerization of the metaformaldehyde that up to the present mixer etc. propose etc.Device. More than the temperature of polymerisation machine preferably remains on 63 DEG C and below 135 DEG C, more preferablyBe 70 DEG C of above and 120 DEG C of following scopes, more preferably 70 DEG C above and 100 DEG C withUnder scope. Delay (reaction) time in polymerisation machine be preferably 0.1 minute above and 30Below minute, more preferably 0.1 minute is above and below 25 minutes, and more preferably 0.1More than minute and below 20 minutes. If the temperature of polymerisation machine and holdup time are above-mentioned modelEnclose, there is the tendency of continual and steady polymerisation.
The polymerization catalyst containing in the polyoxymethylene copolymer obtaining by polymerisationInactivation can contain by input the amines such as ammonia, triethylamine, tri-n-butylamine; Boronic acid compounds class;In the catalyst such as the hydroxide of alkali metal or alkaline-earth metal, inorganic acid salt, acylate and loseIn the aqueous solution and/or organic solvent of agent of living, with the common stirred for several of slurry form minute～a few hoursCarry out. Now, polyoxymethylene copolymer is large when block, after preferred polymeric first by itAfter pulverizing, process. Afterwards, undertaken by filtration drying.
As in catalyst and deactivator, can use separately quaternary ammonium compound or also can be withAbove-mentioned catalysqt deactivation agent use, owing to can more effectively carrying out the neutralization of catalyst and excellentChoosing. In addition, be not particularly limited, preferably by making steam and the polyoxy Asia of ammonia, triethylamine etc.Methyl copolymer contact and make the method for catalysqt deactivation, by make hindered amines, triphenylphosphine,At least a kind and polyoxymethylene copolymerization of calcium hydroxide, boronic acid compounds or quaternary ammonium compound etc.Thing contacts and makes the method for catalysqt deactivation in mixer.
Heat-labile owing to existing in the polyoxymethylene copolymer after polymerization catalyst inactivationEnd portion, therefore implements the decomposition of unstable end portion and removes and stabilisation.
As the method for decomposing and removing of unstable end portion, for example, can enumerate and be included in alkalescenceUnder the existence of material by operation mixing polymer melting and will by decompose produce formaldehyde dischargeThe method of the operation of at least two steps of the operation of removing. As device, preferably use can be continuousThe single-screw extruder with steam vent of the operation of above-mentioned two steps, two with steam vent are implemented in groundScrew extruder etc. As above-mentioned alkaline matter, can enumerate ammonia, triethylamine, tri-n-butylamineDeng amine; The hydroxide of the alkali metal such as calcium hydroxide or alkaline-earth metal, inorganic acid salt, organicHydrochlorate; Quaternary ammonium compound etc. Because the addition with minute quantity can obtain within the utmost point short timeThe polyoxymethylene copolymer of residual unstable end portion hardly, therefore particularly preferably usesQuaternary ammonium compound shown in following formula (4). In addition, above-mentioned alkaline matter can with water, methyl alcohol oneRise and use, the alkaline matter that also two or more kinds may be used.
[R9R10R11R12N+]mX-m···(4)
(in formula, R9、R10、R11、R12Represent independently of one another not getting of carbon number 1～30Substituted alkyl or substituted alkyl; The aryl of carbon number 6～20; Not not getting of carbon number 1～30Aralkyl after substituted alkyl or substituted alkyl are replaced by the aryl of at least 1 carbon number 6～20;The aryl of carbon number 6～20 is by the not substituted alkyl of at least 1 carbon number 1～30 or getAlkylaryl after substituted alkyl replaces, substituted alkyl or substituted alkyl are not straight chain, side chain or ringShape. The substituting group of above-mentioned substituted alkyl is halogen, hydroxyl, aldehyde radical, carboxyl, amino or acid amidesBase. In addition, the hydrogen atom of above-mentioned not substituted alkyl, aryl, aralkyl, alkylaryl is passableReplaced by halogen. M represents 1～3 integer. X represents hydroxyl or carbon number 1～20Beyond carboxylic acid, hydrogen halides containing hydracid, oxyacid, inorganic thio-acid or carbon number 1～20The sour residue of organic thio-acid. )
As quaternary ammonium compound, the represented material of preferred above-mentioned formula (4), in above-mentioned formula (4)R9、R10、R11、R12The more preferably alkyl of carbon number 1～5 or carbon atom independently of one anotherSeveral 2～4 hydroxy alkyl, wherein, R9、R10、R11、R12At least 1 further preferablyFor hydroxyethyl. Particularly, can enumerate tetramethyl-ammonium, tetraethyl ammonium, tetrapropyl ammonium, fourNormal-butyl ammonium, cetyl trimethyl ammonium, myristyl trimethyl ammonium, 1,6-hexa-methylene two (threeAmmonium methyl), decamethylene two (trimethyl ammonium), trimethyl-3-chlorine-2-hydroxyl propyl ammoniums, trimethyl(2-hydroxyethyl) ammonium, triethyl group (2-hydroxyethyl) ammonium, ammonium, three just for tripropyl (2-hydroxyethyl)Butyl (2-hydroxyethyl) ammonium, tri methyl benzyl ammonium, triethyl group hexadecyldimethyl benzyl ammonium, tripropyl hexadecyldimethyl benzyl ammonium,Three normal-butyl hexadecyldimethyl benzyl ammoniums, trimethylphenyl ammonium, triethyl group phenyl ammonium, trimethyl-2-oxygen ethyl ammonium,Monomethyl trihydroxyethyl ammonium, single ethyl trihydroxyethyl ammonium, octadecyl three (2-hydroxyethyl) ammonium,Four (hydroxyethyl) ammonium etc., hydroxide; Hydrochloric acid, hydrobromic acid, hydrofluoric acid etc. are containing hydrohalogenic acid salt;Sulfuric acid, nitric acid, phosphoric acid, carbonic acid, boric acid, chloric acid, acid iodide, silicic acid, perchloric acid, sub-chlorineThe oxysalt of acid, hypochlorous acid, chlorosulfonic acid, sulfamic acid, two sulfuric acid, tripolyphosphate etc.;The thiosalts such as thiosulfuric acid; Formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, ownCarboxylates such as sour, sad, capric acid, benzoic acid, oxalic acid etc. Wherein, preferred hydroxide (OH-)、Sulfate (HSO4-、SO4 2-), carbonate (HCO3 -、CO3 2-), borate (B (OH)4-), carboxylicHydrochlorate. In these carboxylic acids, more preferably formic acid, acetic acid, propionic acid. These quaternary ammonium compounds canUse separately, also can be used in combination two or more. In addition, except above-mentioned quaternary ammonium compound withCan be used together the amine such as ammonia, triethylamine etc. outward.
The addition of quaternary ammonium compound, with respect to polyoxymethylene copolymer, is converted into following mathematicsThe amount of the represented nitrogen from quaternary ammonium compound of formula (5), be preferably 0.05 quality ppm above andBelow 50 quality ppm.
P×14/Q···(5)
(in formula, P represents the concentration (quality of quaternary ammonium compound with respect to polyoxymethylene copolymerPpm), 14 atomic weight that are nitrogen, Q represents the molecular weight of quaternary ammonium compound. )
The addition of quaternary ammonium compound is 0.05 quality ppm when above, unstable terminal part pointSolution is removed speed and can not be reduced, and is 50 quality ppm when following, point the removing of unstable terminal partThe tone of the polyoxymethylene copolymer after going can be not deteriorated. The adding method of quaternary ammonium compound does not haveThere is special restriction, have the form with the aqueous solution in the operation of polymerization catalyst inactivation addedMethod, the method to the oxymethylene copolymer winding-up before melting, the method for adding after meltingDeng, no matter but use any adding method, as long as polymer is deposited in the operation of melt process.
By application aforementioned stable method, unsettled terminal part is considerably less and thermally-stabilised good,Can the short time and obtain easily weather stain and be detained the polyoxymethylene of coloring improvementCopolymer.
The mode of polymerization is not particularly limited, in order easily to obtain polyoxymethylene copolymerPowder, is preferably slurry polymerization, polymerisation in bulk.
<polyacetals particle>
The polyacetals particle of present embodiment is as long as poly-by what obtain by above-mentioned manufacture methodThe shape granulation of acetal is that graininess is just not particularly limited, for example, and by obtaining in extruderTo polyacetals discharge, undertaken by methods such as water-bath are cooling earnestly from the die section of extruderCooling obtaining. In addition, after cooling, can carry out granulating and carry out granulation. Can pass through die sectionSize or shape, size, the shape of suitably controlling the particle obtaining such as fervent.
The size of<particle>
The longest diameter (also referred to as major diameter) of polyacetals particle is preferably below 5mm, more preferablyMore than 2mm and below 5mm. Be the polyacetals particle below 5mm by using major diameter, canSignificantly to reduce the polyacetals particle containing foreign matter. In addition, the shortest diameter (minor axis) of polyacetals particleBe preferably below 4mm, more preferably 1mm is above and below 4mm, more preferably 1mmAbove and below 3mm. By using minor axis for the polyacetals particle below 4mm, in aftermentionedPath on the overlapping situation of more than 2 polyacetals particle tail off, the precision of grain sorting uprises.In addition, on path described later, preferably the minor axis of polyacetals particle be polyacetals particle height,The major diameter of polyacetals particle is and the diameter of the highly orthogonal of polyacetals particle.
The shape of<particle>
The shape of polyacetals particle is as long as be just not particularly limited for graininess, can enumerate oblate spheroid,The shape such as cylindrical, preferably oblate spheroid. By being oblate spheroid, particle is easily arranged and can not be weighedFold, there is the tendency of sorting effectively.
The amount of<formaldehyde>
The amount of the formaldehyde that the polyacetals particle of present embodiment produces by the heating of 100 DEG C isBelow 10 quality ppm, be preferably below 8 quality ppm, more preferably 5 quality ppm withUnder. The amount of the formaldehyde producing by the heating of 100 DEG C is below 10 quality ppm, long thusAfter phase running, paraformaldehyde is not easy to separate out, and easily effectively removes foreign matter. Can be by implementingThe method recorded in example is measured the formaldehyde that the heating of 100 DEG C produces of passing through of polyacetals particleAmount.
The amount of the formaldehyde that the polyacetals particle of present embodiment produces by the heating of 120 DEG C is excellentElect as below 10 quality ppm, more preferably below 8 quality ppm, more preferably 5Below quality ppm. The amount of the formaldehyde producing by the heating of 120 DEG C be 10 quality ppm withUnder, thus can the baking temperature when using after polyacetals particle drying set highlyer and willSet drying time shortlyer, after long-term running, paraformaldehyde is more difficult separates out, and easily more hasRemove to effect foreign matter. Can measure passing through of polyacetals particle by the method for recording in embodimentThe heating of 120 DEG C and the amount of the formaldehyde that produces.
<foreign matter>
From the obstruction, moulding that suppress the mold for forming while carrying out microfabrication, shaping thin wall notThe viewpoint good, mould destroys, the viewpoint that inhibition forms the defect after film, sheet are considered, this realityThe particle that the polyacetals particle of executing mode preferably contains foreign matter is few, even if contain foreign matter, also preferredThe size of foreign matter is little, quantity is few. Foreign matter is not particularly limited, and can enumerate the polymerization by polyacetalsAccessory substance, additive that reaction obtains, from the material of carbide, because certain reason is from bodyThe metallic foreign body from works of carrying secretly in system etc. Foreign matter is during from the material of carbide,Foreign matter easily sends black, the essence of the sorting of the particle that contains foreign matter in sorting operation described laterSpend high.
As long as the foreign matter in present embodiment has from the outward appearance of polyacetals particle by visual passableColor, the size of the degree of confirming, be not particularly limited. For example, the bunching of principal componentAldehyde is transparent material, and on the other hand, the foreign matters wherein containing sees through light, therefore canConfirm. The foreign matter containing in the polyacetals particle obtaining after sorting operation described later is preferably less than1.0mm, is more preferably less than 0.3mm.
Breadth Maximum in polyacetals particle is that the content of foreign matter more than 1.0mm is preferably 20Individual/below kg, more preferably 15/below kg, more preferably 0/kg.
Breadth Maximum is that the number of foreign matter more than 1.0mm can be true by visual 11 groundRecognize the polyacetals particle of 3kg, the temporary transient particle of collecting containing foreign matter, makes this grain dissolution with solvent,Collect undissolved foreign matter, and carry out size up with slide measure.
Breadth Maximum be foreign matter more than 0.3mm be preferably 20/below kg, more preferably maximumWidth be foreign matter more than 0.3mm be 15/below kg, more preferably 0/kg.
Method that can be by below etc. measure Breadth Maximum be more than 0.3mm foreign matterNumber. Make the polyacetals grain dissolution of 3kg in hexafluoroisopropanol, make foreign matter by centrifugal separatorSedimentation, discarded supernatant makes foreign matter disperse, by centrifugation again in hexafluoroisopropanolMachine makes foreign matter sedimentation. Repeatedly after this operation, by using the suction filtration segregating foreign objects of molecular filter.By after dry the foreign matter after separating processing, cross the sieve of screen size 300 μ m, and calculate illogicalThe number of the per unit mass of the foreign matter of crossing.
<granulating working procedure>
The granulating working procedure of present embodiment is as long as by the above-mentioned polyacetals that polymerization obtains that passes throughThe amount of the formaldehyde that granulation is graininess, produce by the heating of 100 DEG C be 10 quality ppm withUnder, be just not particularly limited.
<particle-size distributor>
As the particle-size distributor of present embodiment, as long as there is particle that sorting contains foreign matterFunction is just not particularly limited, and for example, can use and have the regulation of passing through configuration by particlePath reach the particle-size distributor of the formation of above-mentioned functions. Particularly, can enumerate strain formulaCommercial firm's Kubo field foreign matter separator processed, Satake Corp's light separator processed, TECMAN industryCo., Ltd.'s color selector processed etc.
<sorting operation>
The sorting operation of present embodiment needs only as passing through particle-size distributor sorting polyacetals particle,The amount of the polyacetals particle that contains foreign matter with respect to the amount of whole polyacetals particles is for being less than 600 matterThe operation of amount ppm, is just not particularly limited. For example, can make polyacetals particle by above-mentionedParticle-size distributor, the particle separation when detecting coloured foreign matter, only collects containing colouredThe particle etc. of foreign matter. The polyacetals that preferably contains foreign matter with respect to the amount of whole polyacetals particlesThe amount of particle is below 300 quality ppm.
Sorting operation can be by the whole of the polyacetals particle of removing by particle-size distributor or oneDivide the polyacetals recycling as granulating working procedure. Consider it is excellent from the viewpoint of effective utilization of materialChoosing.
As the supply method of the polyacetals particle to particle-size distributor, although depend on that particle dividesSelect the structure of machine, use path and this path with regulation to possess particle but for example can enumerateThe particle-size distributor of sorting function, supplies with polyacetals at this path from top, after grain sorting,Particle free is fallen, the method separating thus etc. With regard to path, from preferably to gatherThe viewpoint that not stacked 11 ground of mode of acetal particle is arranged is considered, is preferably belt conveyingThe path of machine shape. 2 while overlapping above, likely can not bring into play fully grain sorting function.Therefore, preferably on path, possesses more than 2 grain sorting function. Thus, a sortingAfter grain, further make it by possessing the path of other grain sorting function, can manufacture thusHighly purified polyacetals particle.
Feed speed to the polyacetals particle of particle-size distributor is not particularly limited, from productivity ratioViewpoint consider, be preferably more than 1000kg/ hour, more preferably more than 2000kg/ hour,More preferably more than 3000kg/ hour.
Embodiment
Below, enumerate specific embodiment and comparative example explains present embodiment, butPresent embodiment only otherwise exceed its main idea, is just not limited to following embodiment. In addition, belowThe assay method of the various characteristics in embodiment is shown.
(1) mensuration of the foreign matter in polyacetals particle
For polyacetals particle 3kg, the particle that contains foreign matter by visual sorting, then with tripThe size of the foreign matter containing in the particle that contains foreign matter of every 1 particle of mark kind of calliper. Then,The gross weight of the particle that contains foreign matter by measurement, calculates the quality ppm containing foreign particles.Then, under 200 DEG C of pressure at 10MPa, by particle 100g compacting 5 minutes, make 10Open the matrix band of 30cm × 30cm × about 1.2mm, and confirm by visual.
There is the situation of foreign matter more than 1.0mm, be judged to be ×
There is no more than 1.0mm foreign matter, have the situation of foreign matter more than 0.3mm, be judged to be △
There is no more than 0.3mm foreign matter, while having the foreign matter that is less than 0.3mm, number goes out number, closesCount 30 above situations, be judged to be zero
Situation in addition, is judged to be ◎.
(2) evaluation of lock out operation
In sorting operation, the lock out operation that can carry out for every 1 hour more than 3000kg is considered as separatingOperability is very high, is evaluated as ◎.
Be considered as point within every 1 hour, carrying out 1000kg lock out operation above and that be less than 3000kgHigh from operability, be evaluated as zero.
Every lock out operation that can only be less than 1000kg for 1 hour is considered as to lock out operation low,Be evaluated as ×.
The average evaluation that run stability is gone wrong is △.
(3) formaldehyde in polyacetals particle
The following amount of measuring the formaldehyde producing by the heating of 100 DEG C or 120 DEG C. There is valveTedlar (registration mark) bag in pack 20.00g polyacetals particle into, fully carry out nitrogen replacementAfter, in Tedlar (registration mark) bag, enclose 5.00L nitrogen. Afterwards, on inner top,In the baking oven with the sample tap connecting with outside, put into Tedlar (registration mark) bag and be connected and getSample bag is then placed 1 hour at the temperature of 100 DEG C or 120 DEG C. Afterwards, connect at sample tapConnect DNPH filter core, open the valve of sampling bag, make 4.00L gas by DNPH filter core. WithConstant speed makes the acetonitrile of 5mL by DNPH filter core, and formaldehyde is recovered in to 10mL measuring bottle.Add afterwards water to 10mL, fully mix. The liquid dispensing of this mixing is entered to sampling bottle, useThe HPLC processed of Shimadzu Seisakusho Ltd., titer uses DNPH titer, and parting liquid makes water/acetonitrile(52/48), carry out quantitatively, having measured every particle with ppm with 40 DEG C of flow 1mL/ minutes, column temperatureThe formaldehyde of mass formation. Determination of the upper limit is below 15ppm, will exceed the situation note of determination of the upper limitFor O.D..
(4) size of polyacetals particle
For maximum gauge and the minimum diameter of polyacetals particle, use slide measure to measure 100Individual polyacetals particle, by average obtaining.
[Production Example of polyacetals particle]
(POM-1)
The polymerization machine of twin-screw self-cleaning type of jacketed of thermal medium of can circulating is adjusted to 80DEG C, within 12kg/ hour, adding continuously metaformaldehyde, with 414.6g/ hour (with respect to trimerization first1 mole, aldehyde is 4.2 % by mole) add continuously as 1 of comonomer, 3-dioxolane,With respect to 1 mole of dimethoxym ethane adding continuously as chain-transferring agent using 6.8g/ hour of metaformaldehyde.In addition, add continuously the boron trifluoride di-n-butyl etherate 1 quality % as polymerization catalystCyclohexane solution 38g/ hour, and carry out polymerization. The mode of polymerization is polymerisation in bulk. Will be byThe powder of the Copolyacetal that polymerization machine is discharged drops in triethylamine 0.1% aqueous solution and gathersClose the inactivation of catalyst. With the Copolyacetal after centrifugal separator filtration inactivation, after cleaningBe dried at 140 DEG C, thereby obtain thick polyacetals.
Afterwards, add the water containing as trimethyl-2-hydroxyethyl ammonium formate of quaternary ammonium compoundSolution 1 mass parts, as the two [3-(the 3-tert-butyl group-5-methyl-4-hydroxyls of the triethylene glycol of antioxidantPhenyl) propionic ester] 0.3 mass parts, calcium stearate 0.2 mass parts, to the twin-screw with steam ventFormula extruder is supplied with. Add 5 % by weight triethylamine aqueous solutions to the polyacetals of melting in extruder2 mass parts, are set as 200 DEG C by the design temperature of extruder, carry out dividing of unstable terminal partSeparate. Gathering after unstable terminal part being decomposed under the condition of then, holding in the palm in steam vent vacuum 20Acetal devolatilization, is discharged by extruder die head. By fervent the polyacetals of discharging from die sectionRear water-bath is cooling, thereby obtains polyacetals particle.
In extruding, under the condition that is 100rpm at the rotating speed of screw rod, turn round, start 10 from runningAfter hour, start the manufacture of POM-1, within every 10 minutes, make rotating speed be suitably changed to 50rpm,100rpm, 150rpm, regulate the grain amount that contains foreign matter in polyacetals particle thus. ObtainPolyacetals particle in the amount of the particle that contains foreign matter be 1200ppm, contain and have thereinThe foreign matter of size more than 1mm.
(POM-2)
The line material of the polyacetals of discharging from die section is cooling with water-bath, then granulation, except this withObtain polyacetals particle by the method same with the manufacture method of POM-1 outward. ObtainThe amount of the particle that contains foreign matter in polyacetals particle is 1200ppm, contains and has thereinThe foreign matter of size more than 1mm.
(POM-3)
In the thick polyacetals obtaining, do not add quaternary ammonium compound, add 2,2-di-2-ethylhexylphosphine oxide (4-firstBase-tert-butyl phenol) 0.3 mass parts replace triethylene glycol two-[3-(the 3-tert-butyl group-5-methyl-4-hydroxylPhenyl) propionic ester] as antioxidant, in addition, by same with the manufacture method of POM-1The method of sample has obtained polyacetals particle. The particle that contains foreign matter in the polyacetals particle obtainingAmount be 1200ppm, contain therein the foreign matter with size more than 1mm.
[particle-size distributor]
In embodiment described later and comparative example, use the foreign matter separator of Satake Corp's system:Goods name PCS600BFD type.
(embodiment 1)
Use foreign matter separator to carry out lock out operation to POM-1, make it with about 1000kg/ hourSpeed pass through.
On the path that possesses particle-size distributor, particle is arranged in nonoverlapping mode. Can beginStably process eventually particle. In result shown in table 1.
(embodiment 2～4)
Except the condition shown in table 1, implement similarly to Example 1. In table 1Result is shown.
(embodiment 5)
For POM-2, use foreign matter separator to carry out lock out operation, make it with about 1000kg/Hour speed pass through. In result shown in table 1.
(embodiment 6～8)
Except the condition shown in table 1, implement similarly to Example 5. In table 1Result is shown.
(comparative example 1)
To the particle 3kg of POM-1 by the visual lock out operation that carried out. Time needs 1 hour.In result shown in table 2.
(comparative example 2)
To the particle 3kg of POM-2 by the visual lock out operation that carried out. Time needs 1 hour.In result shown in table 2.
(comparative example 3)
Except using POM-3, carry out lock out operation similarly to Example 1. At tableResult shown in 2.
(comparative example 4)
The polymerization machine of the twin-screw self-cleaning type with the thermal medium that can circulate is adjusted to 80 DEG C,Within 12kg/ hour, adding continuously metaformaldehyde, with 414.6g/ hour (with respect to metaformaldehyde 1Mole be 4.2 % by mole) add continuously as 1 of comonomer 3-dioxolane, relativelyIn 1 mole of dimethoxym ethane adding continuously as chain-transferring agent using 6.8g/ hour of metaformaldehyde. SeparatelyAdd continuously the boron trifluoride di-n-butyl etherate 1 quality % as polymerization catalyst outward,Cyclohexane solution 38g/ hour and carry out polymerization. The mode of polymerization is polymerisation in bulk. Will be by gatheringThe powder of the Copolyacetal that the machine that closes is discharged drops in triethylamine 0.1% aqueous solution and carries out polymerizationThe inactivation of catalyst. Filter the Copolyacetal of inactivation with centrifugal separator, after cleaning 140DEG C dry, thus thick polyacetals obtained.
Afterwards, add the water containing as trimethyl-2-hydroxyethyl ammonium formate of quaternary ammonium compoundSolution 1 mass parts, as 2 of antioxidant, 2-di-2-ethylhexylphosphine oxide (4-methyl-tert-butyl phenol) 0.3Mass parts, calcium stearate 0.2 mass parts to possessing screen cloth (#200 with steam vent on porous plateOrder) double-screw type extruder supply with. In the polyacetals of melting in extruder, add 5 weight% triethylamine aqueous solution 2 mass parts, are set as 200 DEG C by the design temperature of extruder, have carried outThe decomposition of unstable terminal part. Under the condition of then, holding in the palm in steam vent vacuum 20 by unstablePolyacetals devolatilization after terminal part decomposes, and discharged by extruder die head. Will be from die headThe earnestly rear water-bath of the polyacetals that portion discharges is cooling, thereby obtains polyacetals particle.
In extruding, under the condition that is 100rpm at the rotating speed of screw rod, turn round, start 10 from runningAfter hour, start to gather polyacetals particle, within every 10 minutes, make rotating speed be suitably changed to 50rpm,100rpm, 150rpm. In result shown in table 2.
(comparative example 5)
Except changing fervent speed, changing the size of particle, with the manufacturer of POM-1Method is similarly implemented. In result shown in table 2.
As shown in table 1, in embodiment 1～8, be below 600ppm containing the grain amount of foreign matter,Therefore known its is high-quality. In addition, can carry out lock out operation with 1000kg/ hour, thereforeCan effectively obtain polyacetals particle.
Do not use particle-size distributor and by the visual comparative example 1 and 2 that carries out foreign matter sorting,Can obtain the few polyacetals particle of particle that contains foreign matter in polyacetals particle, but can not obtainTo good lock out operation in practicality.
In comparative example 3, the heat endurance of polyacetals particle is low, and therefore supposition is because produceThe impact of formaldehyde, can not carry out lock out operation well.
Comparative example 4 and 5 does not carry out lock out operation, therefore in polyacetals particle, sneaks into a large amount ofThe particle that contains foreign matter.
[table 1]
[table 2]
Industrial applicability
The manufacture method of polyacetals particle of the present invention is at electric and electronic Material Field, automobile neckVarious component materials, film/sheet material, machinery in territory, other various industrial materials field etc.Or there is industry in the field such as small formed product material, the packaging material of food using in devicePracticality.

Claims (9)

1. a manufacture method for polyacetals particle, it comprises following operation:
Granulating working procedure, obtain heating by 100 DEG C by the polyacetals obtaining by polymerization andThe amount of the formaldehyde producing is the polyacetals particle below 10 quality ppm; With
Sorting operation, utilizes particle-size distributor to carry out sorting to described polyacetals particle, therebyAmount to the polyacetals particle that contains foreign matter with respect to the amount of whole polyacetals particles is less than 600 matterThe polyacetals particle of amount ppm.
2. the manufacture method of polyacetals particle as claimed in claim 1, wherein, described foreign matterFor deriving from the foreign matter of carbide.
3. the manufacture method of polyacetals particle as claimed in claim 1 or 2, wherein, described inPolyacetals particle be shaped as oblate spheroid.
4. the manufacture method of the polyacetals particle as described in any one in claim 1～3, itsIn, the longest diameter of described polyacetals particle is that 5mm is following, the shortest diameter is below 3mm.
5. the manufacture method of the polyacetals particle as described in any one in claim 1～4, itsIn, described foreign matter is less than 1.0mm.
6. the manufacture method of the polyacetals particle as described in any one in claim 1～5, itsIn, described sorting operation is whole by the polyacetals particle that utilizes described particle-size distributor to removeOr a part is as the sorting operation of the polyacetals recycling of described granulating working procedure.
7. the manufacture method of the polyacetals particle as described in any one in claim 1～6, itsIn, described foreign matter is less than 0.3mm,
Described sorting operation is the bunching obtaining with respect to containing foreign matter described in polyacetals particle total amountThe amount of aldehyde particle is the sorting operation of the polyacetals particle below 300 quality ppm.
8. the manufacture method of the polyacetals particle as described in any one in claim 1～7, itsIn, described granulating working procedure is that the amount that obtains the formaldehyde producing by the heating of 120 DEG C is 10 matterThe granulating working procedure of the polyacetals particle of the polyacetals below amount ppm.
9. a polyacetals particle, it is by the manufacture described in any one in claim 1～8Method and obtaining.
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