CN105599169B - The manufacturing method of polyacetals particle - Google Patents

The manufacturing method of polyacetals particle Download PDF

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CN105599169B
CN105599169B CN201510779519.9A CN201510779519A CN105599169B CN 105599169 B CN105599169 B CN 105599169B CN 201510779519 A CN201510779519 A CN 201510779519A CN 105599169 B CN105599169 B CN 105599169B
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polyacetals
particle
acid
foreign matter
manufacturing
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CN105599169A (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 Kogyo KK
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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 present invention relates to the manufacturing methods of polyacetals particle.The present invention provides the manufacturing method that can manufacture the polyacetals particle of the polyacetals particle of high-purity of few foreign.A kind of manufacturing method of polyacetals particle comprising following process: granulating working procedure, the amount as obtaining the formaldehyde generated by 100 DEG C of heating by polyacetals obtained from polymerization are 10 mass ppm polyacetals particle below；With sorting process, above-mentioned polyacetals particle is sorted by particle-size distributor, so that the amount for obtaining the polyacetals particle for containing foreign matter relative to the amount of whole polyacetals particles is less than the polyacetals particle of 600 mass ppm.

Description

The manufacturing method of polyacetals particle
Technical field
The present invention relates to the manufacturing methods of polyacetals particle.
Background technique
The processability and productivity of polyacetals are excellent, therefore have and can be formed by melt injection molding, melting extrusion Equal forming methods effectively produce the advantages of product of desired shape, component.The advantage that utilization, polyacetals are used extensively It is led in electric and electronic Material Field, automotive field, various other industrial materials fields, food packaging applications, component with material Domain.For these purposes, from appearance design height and there are thin molded articles etc. to consider, it is expected that coloured few foreign, purity High polyacetals.
In order to reduce the foreign matter after molding using heating processing etc., consider to reduce to the greatest extent the sides such as the ingredient other than polyacetals Method, but for thermal stability, mechanical strength, mechanical strength stabilisation etc., it is necessary to the addition for the reason of being likely to become foreign matter is added Agent.Therefore, it is proposed to inhibit the technology of the generation of foreign matter by the composition for designing the additive added into polyacetals.
For example, can enumerate: being combined with antioxidant and oxide selected from magnesium or calcium or one or more of carbonate The polyacetals (for example, citation 1) of metalliferous compound, polyalkylene glycol；Comprising polyacetals and selected from by poly- (N- second Alkene-carboxylic acid's amide) and the group that forms of copolymer of N- Vinylcarboxylic acid amide and other vinyl monomers in it is at least one kind of, With the ester selected from ester, alcohols and dicarboxylic acids by polyalkylene glycol and its derivative, fatty acid amide, alcohols and fatty acid The polyacetals (for example, patent document 2) of at least one of the group of composition.
In addition, can enumerate as the method for removing the foreign matter in polymer in order to when using the injection moulding of hot flow path Metallic foreign body is inhibited to block hot flow path, (only taking-up metal is mixed into few for injection molding particle with magnetic grader sorting Particle) technology (for example, patent document 3), from resin particle remove colored particles technology (for example, patent document 4).
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 7-228751 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2001-247745 bulletin
Patent document 3: Japanese Unexamined Patent Publication 2004-99682 bulletin
Patent document 4: Japanese Unexamined Patent Publication 2-253891 bulletin
Summary of the invention
Problem to be solved by the invention
However, for polyacetals disclosed in above patent document 1,2, not about the control of resin viscosity, system The record of the influence of the variation for the amount of making etc..In addition, the technology of above patent document 3 specifically makes resin particle pass through magnetic force The technology of sorting machine cannot utilize sufficiently except the metal for including inside degranulation additionally, due to the particle once adsorbed by magnet Self weight and later by the collision of particle fall reasons, the removing of foreign matter (metal) such as cannot to completely remove and do not fill Point.The technology of patent document 4 describes the removing method of the foreign matter in particle, but not to the state of its optimum particle into Row is recorded, and does not in addition also refer to polyacetals particle.
Therefore, the purpose of the present invention is to provide the polyacetals of the polyacetals particle for the high-purity that can manufacture few foreign The manufacturing method of grain.The purpose of the present invention, which is furthermore that, provides a kind of manufacturing method of polyacetals, can effectively inhibit The generation of black foreign matter when melt-processed, can effectively manufacture the polyacetals of high-purity.
The means used to solve the problem
The inventors of the present invention have made intensive studies to solve above-mentioned problem of the prior art, as a result, it has been found that, pass through benefit Polyacetals particle is manufactured with the manufacturing method with specific granulating working procedure and specific sorting process, available few foreign The polyacetals particle of high-purity, so as to complete the present invention.
That is, the present invention is as described below.
[1] a kind of manufacturing method of polyacetals particle comprising following process:
Granulating working procedure, as obtaining the amount of the formaldehyde generated by 100 DEG C of heating by polyacetals obtained from polymerization For 10 mass ppm polyacetals particle below；With
Process is sorted, above-mentioned polyacetals particle is sorted by particle-size distributor, to obtain relative to all poly- The amount that the amount of acetal particle contains the polyacetals particle of foreign matter is less than the polyacetals particle of 600 mass ppm.
[2] manufacturing method of the polyacetals particle according to [1], wherein above-mentioned foreign matter is from the different of carbide Object.
[3] manufacturing method of the polyacetals particle according to [1] or [2], wherein the shape of above-mentioned polyacetals particle is Oblate spheroid.
[4] manufacturing method of the polyacetals particle according to any one of [1]~[3], wherein above-mentioned polyacetals particle Longest diameter be 5mm or less, most short diameter is 3mm or less.
[5] manufacturing method of the polyacetals particle according to any one of [1]~[4], wherein above-mentioned foreign matter is less than 1.0mm。
[6] manufacturing method of the polyacetals particle according to any one of [1]~[5], wherein above-mentioned sorting process is Again using all or part of of the polyacetals particle removed using above-mentioned particle-size distributor as the polyacetals of above-mentioned granulating working procedure The sorting process utilized.
[7] manufacturing method of the polyacetals particle according to any one of [1]~[6], wherein above-mentioned foreign matter is less than 0.3mm,
Above-mentioned sorting process is to obtain being relative to the amount of the above-mentioned polyacetals particle containing foreign matter of polyacetals particle total amount The sorting process of 300 mass ppm polyacetals particle below.
[8] manufacturing method of the polyacetals particle according to any one of [1]~[7], wherein above-mentioned granulating working procedure is The amount of the formaldehyde generated by 120 DEG C of heating is obtained as the granulation of the polyacetals particle of 10 mass ppm polyacetals below Process.
Invention effect
The manufacturing method of polyacetals particle according to the present invention can manufacture the polyacetals particle of the high-purity of few foreign.
Specific embodiment
Hereinafter, being explained in detail to mode for carrying out the present invention (hereinafter referred to as " present embodiment ").Below Embodiment is for illustrating illustration of the invention, and the present invention is not limited to contents below.The present invention can be in the model of its main idea Implement after enclosing interior progress various modifications.
The manufacturing method of the polyacetals particle of present embodiment includes following process:
Granulating working procedure, as obtaining the amount of the formaldehyde generated by 100 DEG C of heating by polyacetals obtained from polymerization For 10 mass ppm polyacetals particle below；With
Process is sorted, above-mentioned polyacetals particle is sorted by particle-size distributor, to obtain relative to polyacetals The amount that the total amount of particle contains the polyacetals particle of foreign matter is less than the polyacetals particle of 600 mass ppm.
<polyacetals>
Polyacetals in present embodiment can be enumerated: pass through the cyclic oligomers such as formaldehyde, metaformaldehyde or four polyformaldehyde Substantially by oxymethylene units-(CH obtained from homopolymerization2O)-constitute polyoxymethylene homopolymer or by formaldehyde and/ Or metaformaldehyde, with cyclic ether and/or cyclic formals, be added with 1 mass ppm or more and the 500 following Hinered phenols of mass ppm Have obtained from the copolymerization of the cyclic formals of antioxidant and is including oxymethylene units-(CH2O)-chain in randomly The polyoxymethylene copolymer etc. of structure inserted with oxygen alkylidene unit represented by the following general formula (1).
(the R in formula1And R2Respectively hydrogen atom, alkyl or aryl, they can be the same or different, and n is 2~6 Integer)
It is also sub- comprising the branch polyoxy after strand collateralization in polyoxymethylene copolymer used in present embodiment Methyl copolymer and sub- with the polyoxy of the variety classes ingredient block of the oxymethylene repeat units containing 50 mass % or more Methyl block copolymer.
In addition, the insertion rate of the above-mentioned oxygen alkylidene unit in polyoxymethylene copolymer is relative to oxymethylene units 100 moles preferably 0.01 mole or more and 50 moles hereinafter, more preferably 0.03 mole or more and 20 moles of ranges below.Make For the oxygen alkylidene unit, such as more oxygen ethylene unit, oxygen propylene unit, oxygen tetramethylene unit, oxygen butylidene can be enumerated Unit, oxygen phenyl-ethylene unit etc..In these oxygen alkylidene units, in terms of improving the physical property of polyacetal resin composite Consider, preferably more oxygen ethylene unit-[(CH2)2O]-and oxygen tetramethylene unit-[(CH2)4O]-。
The polyacetals as obtained from above-mentioned homopolymerization or copolymerization preferably carries out the stabilization processes of molecular end.As molecule The stabilization treatment method of end, can be used for example by the methods of the hydroxy esterification of end, etherificate, urethane or By the unstable part of molecular end by hydrolyzing stabilized method etc..
For example, can be by: the copolymerization of formaldehyde and/or metaformaldehyde and cyclic ether and/or cyclic formals will be passed through Obtained polyoxymethylene copolymer carries out the process of the stabilization processes of molecular end, later in molten immediately after polymerisation The process that injection water or alcohol or their mixture and mixing can be implemented and the above-mentioned water by injection are continuously supplied under state The different directions of the devolatilization process of the steam and free Form aldehyde release of equal hydroxy-containing compounds rotate the double spiral shells of non-occlusive type Bar extruder simultaneously handle etc. and obtain such polyacetals.In addition, injecting above-mentioned water or alcohol or their mixture And when being kneaded, the preferably alkaline matters such as addition triethylamine are as pH adjusting agent.
It, within the scope of the effect without prejudice to the mode of implementation, can independent or group in the polyacetals of present embodiment It closes using additive, such as heat stabilizer, weather-proof (light) stabilizer, release agent used in previous polyacetals etc..
As heat stabilizer, the agent for capturing of antioxidant, formaldehyde or formic acid or being used in combination for they can be enumerated, it is preferably anti-oxidant Agent is used in combination with agent for capturing.
As antioxidant, preferably hindered phenol anti-oxidants, such as 3- (3 ', 5 '--4 '-hydroxyls of di-t-butyl can be enumerated Phenyl) n-octadecyl propionate, 3- (3 '--4 '-hydroxy phenyl of methyl -5- tert-butyl) n-octadecyl propionate, 3- (3 ', 5 '--4 '-hydroxy phenyls of di-t-butyl) propionic acid n-tetradecane base ester, bis- (3- (3, the 5- di-t-butyl -4- hydroxyls of 1,6- hexylene glycol Phenyl) propionic ester), 1,4-butanediol bis- (3- (3,5- di-tert-butyl-hydroxy phenyl)-propionic esters), the bis- (3- of triethylene glycol (3- tert-butyl -5- methyl -4- hydroxy phenyl) propionic ester), four (methylene -3- (3 ', 5 '--4 '-hydroxy phenyl of di-t-butyl) Propionate methane, 3,9- bis- (2- (3- (3- tertiary butyl-4-hydroxy -5- aminomethyl phenyl) propionyloxy) -1,1- dimethyl ethyls) - 2,4,8,10- tetra- oxaspiro (5.5) hendecanes, N, the bis- -3- of N '-(3 ', 5 '-di-t-butyl -4- hydroxyl phenol) propiono six are sub- Methanediamine, N, double -3- (3 '--5 '-tertiary butyl-4-hydroxy phenol of methyl) the propiono diamines, N of N '-tetramethylene, N '-is 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, bis- (2- (3- (3,5- dibutyl -4- hydroxy phenyl) propionyloxy) ethyl) hydroxy amides of N '-etc..
In these hindered phenol anti-oxidants, the preferably bis- (3- (3 tert-butyl -5- methyl -4- hydroxy phenyl)-of triethylene glycol Propionic ester), four (methylene -3- (3 ', 5 '--4 '-hydroxy phenyl of di-t-butyl) propionate methanes.
As formaldehyde, the agent for capturing of formic acid, specifically, (a) can be enumerated containing formaldehyde reactivity nitrogen compound and gathered Close object, the hydroxide of (b) alkali or alkaline earth metal, inorganic acid salt, carboxylate and alkoxide etc..
Contain formaldehyde reactivity nitrogen compound as (a), specifically, (1) dicyandiamide can be enumerated, (2) amino replaces Triazine, (3) amino replace triazine and the cocondensation of formaldehyde etc..As (2) amino replace triazine, specifically, have guanamines (2, 4- diamino s-triazine), melamine (2,4,6- tri-amino-p-triazine), N- melamine-butyl, N phenyl melamine, N, N- diphenyl melamine, N, N- diallyl melamine, N, N ', N "-triphenyl melamine, N- methylol melamine Amine, N, (2,4- diamino -6- phenyl are equal for N '-dihydroxymethyl melamine, N, N ', N "-trimethylol melamine, benzoguanamine Triazine), 2,4- diamino -6- methyl s-triazine, 2,4- diamino -6- butyl s-triazine, 2,4- diamino -6- benzyloxy equal three Piperazine, 2,4- diamino -6- butoxy s-triazine, 2,4- diamino -6- cyclohexyl s-triazine, 2,4- diamino -6- chloro-s-triazine, 2,4- diamino -6- sulfydryl s-triazine, 2,4- dihydroxy -6- amino s-triazine (ア メ ラ イ ト), 2- hydroxyl -4,6- diamino S-triazine (ア メ リ Application), N, N, N ', N '-four cyano ethyl benzoguanamine etc..Replace the cocondensation of triazine and formaldehyde as (3) amino Object is closed, specifically, there are melamine-formaldehyde condensation products etc..Among them, preferably dicyandiamide, melamine and melamine- Formaldehyde condensation products.
There is the polymer of formaldehyde reactive nitrogen base as (a), specifically, (1) polyamide can be enumerated, (2) are incited somebody to action Acrylamide and its derivative or acrylamide and its derivative polymerize in the presence of metal alkoxide with other vinyl monomers Obtained from polymer, (3) acrylamide and its derivative or acrylamide and its derivative and other vinyl monomers are existed Polymer, (4) amine, amide, urea and carbamate obtained from polymerizeing in the presence of free radical polymerization etc. is poly- containing nitrogen base Close object etc..As the polyamide of (1), specifically, nylon 4-6, nylon 6, nylon 6-6, nylon 6-10, nylon can be enumerated 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) propylene Amide and its derivative or acrylamide and its derivative polymerize in the presence of metal alkoxide with other vinyl monomers and are obtained The polymer arrived, specifically, poly- Beta-alanine copolymer etc. can be enumerated.Japanese Patent Publication No. 6-12259, day can be passed through The method that this fairness 5-87096, Japanese Patent Publication 5-47568 and Japanese Unexamined Patent Publication 3-234729 each bulletin are recorded Manufacture these polymer.The method that can be recorded by Japanese Unexamined Patent Publication 3-28260 bulletin manufactures (3) for acrylamide and its Derivative or acrylamide and its derivative gather obtained from polymerizeing in the presence of free radical polymerization with other vinyl monomers Close object.
As the hydroxide of (b) alkali or alkaline earth metal, inorganic acid salt, carboxylate and alkoxide, specifically, can lift The hydroxide of sodium, potassium, magnesium, calcium or barium etc., the carbonate of the metal, phosphate, silicate, borate, carboxylate out.The carboxylic The carboxylic acid of hydrochlorate is saturation or unsaturated aliphatic carboxylic acid etc. with 10~36 carbon atoms, these carboxylic acids can be taken by hydroxyl Generation.As representative examples of saturated aliphatic carboxylic, can enumerate capric acid, lauric acid, myristic acid, palmitinic acid, stearic acid, arachidic acid, behenic acid, Tetracosanoic acid, cerinic acid, montanic acid, melissic acid, ceroplastic acid.Unsaturated aliphatic carboxylic acid can enumerate undecenoic acid, oleic acid, anti- Oleic acid, docosenoic acid, erucic acid, brassidic acid, sorbic acid, linoleic acid, linolenic acid, arachidonic acid, propiolic acid, stearic alkynes Acid etc..In addition, methoxide, ethylate of above-mentioned metal etc. can be enumerated as alkoxide.
As weather-proof (light) stabilizer, preferably (a) benzotriazole substance, (b) oxanilide substance and (c) hindered amine Substance.
As (a) benzotriazole substance, specifically, 2- (2 '--5 '-methylphenyl of hydroxyl) benzo three can be enumerated Azoles, 2- [2 '-hydroxyl -3,5- di-t-butyls-phenyl) benzotriazole, 2- [2 '-hydroxyl -3,5- diisoamyl-phenyl] benzo three Azoles, 2- [2 '-hydroxyls -3,5- bis--(alpha, alpha-dimethylbenzyl) phenyl] -2H- benzotriazole, 2- (2 '--4 '-octyloxy benzene of hydroxyl Base) benzotriazole etc., preferably 2- [2 '-hydroxyls -3,5- bis--(alpha, alpha-dimethylbenzyl) phenyl] -2H- benzotriazole, 2- [2 '-hydroxyl -3,5- di-t-butyls-phenyl) benzotriazole.
As (b) oxanilide substance, specifically, 2- ethyoxyl -2 '-ethyloxanilide, 2- second can be enumerated Oxygroup -5- tert-butyl -2 '-ethyloxanilide, 2- ethyoxyl -3 '-dodecyl butoxanilide etc..These substances can be with It is respectively used alone, two or more can also be applied in combination.
As (c) hindered amines substance, specifically, 4- acetoxyl group -2,2 can be enumerated, 6,6- tetramethyl piperidines, 4- are hard Acyl oxygroup -2,2,6,6- tetramethyl piperidines, 4- acryloxy -2,2,6,6- tetramethyl piperidines, 4- (phenylacetyl oxygroup) - 2,2,6,6- tetramethyl piperidines, 4- benzoyloxy -2,2,6,6- tetramethyl piperidines, 4- methoxyl group -2,2,6,6- tetramethyl piperazines Pyridine, 4- tristearin oxygroup -2,2,6,6- tetramethyl piperidines, 4- cyclohexyloxy -2,2,6,6- tetramethyl piperidines, 4- benzyloxy -2,2, 6,6- tetramethyl piperidines, 4- phenoxy group -2,2,6,6- tetramethyl piperidines, 4- (ethylcarbamoyl oxygroup) -2,2,6,6- tetramethyls Phenylpiperidines, 4- (cyclohexyl carboxyamide oxygroup) -2,2,6,6- tetramethyl piperidines, 4- (phenylcarbamoyl oxygroup) -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, oneself Diacid two (2,2,6,6- tetramethyl -4- piperidyl) (ester), terephthalic acid (TPA) two (2,2,6,6- tetramethyl -4- piperidyl) ester, 1,2- bis- (2,2,6,6- tetramethyl -4- piperidyl oxygroup)-ethane, α, bis- (2,2,6, the 6- tetramethyl -4- piperidyl oxygen of α ' - Base)-paraxylene, Toluene-2,4-diisocyanate, 4- diamino acid two (2,2,6,6- tetramethyl -4- piperidyl) ester, hexa-methylene -1,6- bis- Carbamic acid two (2,2,6,6- tetramethyl -4- piperidyl) ester, benzene -1,3, (2,2,6, the 6- tetramethyl -4- piperidines of 5- tricarboxylic acid three Base) ester, benzene -1,3,4- tricarboxylic acid three (2,2,6,6- tetramethyl -4- piperidyl) ester etc., preferably decanedioic acid two (2,2,6,6- Tetramethyl -4- piperidyl) -ester.Above-mentioned hindered amines substance can respectively be used alone, two or more can also be applied in combination.Separately Outside, the more preferably combination of above-mentioned benzotriazole substance, oxanilide substance and hindered amines substance.
As release agent, the ester of alcohol and alcohol and fatty acid, the ester of alcohol and dicarboxylic acids, silicone oil etc. can be enumerated.
As alcohol, specifically, have monohydric alcohol, polyalcohol, such as the example of monohydric alcohol, octanol, just pungent can be enumerated Alcohol (one Le of カ プ リ Le ア Le U), nonyl alcohol, decyl alcohol, tip-nip, laruyl alcohol, tridecanol, myristyl alcohol, pentadecanol, whale Ceryl alcohol, heptadecanol, stearyl alcohol, oleyl alcohol, nonadecanol, eicosanol, docosyl alcohol, ceryl alcohol, melissyl alcohol, 2- hexyl decyl alcohol, 2- Octyldodecanol, 2- decyl alkanol, synthctic fat race alcohol (one Le of ユ ニ リ ソ ア Le U) etc..As polyalcohol, for containing There is the polyalcohol of 2~6 carbon atoms, such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, fourth can be enumerated Glycol, pentanediol, hexylene glycol, glycerol, two glycerol, triglycerin, threitol, erythrite, pentaerythrite, arabitol, ribitol, wood Sugar alcohol, sorbierite, anhydrosorbitol, D-sorbite, mannitol etc..
As the ester of alcohol and fatty acid, in fatty acid cpds, preferably by being selected from palmitinic acid, stearic acid, behenic acid, lignite Fatty acid in acid and fatty acid derived from the polyalcohol in glycerol, pentaerythrite, anhydrosorbitol, D-sorbite Ester.These fatty acid ester compounds may exist hydroxyl, hydroxyl can also be not present, there is no limit to fatty acid ester compound. For example, can may be diester, three esters for monoesters.Furthermore it is possible to will be hydroxy-end capped with boric acid etc..
As preferred aliphatic ester, specifically, glycerol monopalmitate, dipalmitin, glycerol can be enumerated Tripalmitate, glyceryl monostearate, glycerol distearate, glycerol tristearate, Glyceryl monobehenate, glycerol two Behenate, glycerol tri-docosanoic acid ester, glycerol list montanate, two montanate of glycerol, three montanate of glycerol, pentaerythrite Monopalmitate, pentaerythrite dipalmitate, pentaerythrite tripalmitate, four palmitate of pentaerythrite, pentaerythrite Monostearate, pentaerythritol stearate, pentaerythrite tristearate, pentaerythritol tetrastearate, pentaerythrite Single behenate, two behenate of pentaerythrite, pentaerythrite tribehenin acid esters, four behenate of pentaerythrite, pentaerythrite Single montanate, two montanate of pentaerythrite, three montanate of pentaerythrite, four montanate of pentaerythrite, Sorbitan Monoplamitate, anhydrosorbitol dipalmitate, anhydrosorbitol tripalmitate, anhydrosorbitol list are hard Resin acid ester, sorbitandistearate, anhydrosorbitol tristearate, anhydrosorbitol list behenate, Two behenate of anhydrosorbitol, anhydrosorbitol tribehenin acid esters, anhydrosorbitol list montanate, Sorbitan Two montanate of sugar alcohol, three montanate of anhydrosorbitol, sorbitan monopalmitate, D-sorbite dipalmitate, D-sorbite tripalmitate, sorbitan monostearate, sorbitan distearte, D-sorbite tristearate, D-sorbite list behenate, two behenate of D-sorbite, D-sorbite tribehenin acid esters, D-sorbite list montanate, Two montanate of D-sorbite, three montanate of D-sorbite etc..
In addition, fatty acid monoglyceride can also be enumerated as the aliphatic ester compound after will be hydroxy-end capped with boric acid etc. Borate.For the ester of alcohol and dicarboxylic acids, the methanol as alcohol, ethyl alcohol, propyl alcohol, n-butanol, isobutanol, uncle can be enumerated Butanol, n-amyl alcohol, 2- amylalcohol, n-heptanol, n-octyl alcohol, n-nonyl alcohol, laruyl alcohol, myristyl alcohol, cetanol, stearyl alcohol, docosyl alcohol Etc. saturations/unsaturated alcohol with as the oxalic acid of dicarboxylic acids, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, pungent two Monoesters, diester of acid, azelaic acid, decanedioic acid, heneicosanedioic acid, tridecandioic acid, maleic acid, fumaric acid, glutaconate etc. etc..
[manufacturing method of polyacetals]
Single screw rod with gas vent or twin-screw can be used in the manufacturing method of polyacetals as present embodiment Extruder carries out melting mixing to manufacture.As described above, polyacetals is polyoxymethylene homopolymer, polyoxymethylene copolymer Deng.
[manufacturing method of polyacetals: polyoxymethylene homopolymer]
Polyoxymethylene homopolymer is to be obtained by the homopolymerization of the cyclic oligomers such as formaldehyde or metaformaldehyde, four polyformaldehyde That arrives is substantial by oxymethylene units-(CH2O it is to pass through ester that)-composition polyoxymethylene, which is two ends of polymer chain, Homopolymer after base or ether sealing end.Such as it can be using formaldehyde and well known molecular weight regulator as raw material, using well knownThe polymerization catalyst of salt regard hydrocarbon etc. as solvent, passes through well known slurry method, such as Japanese Patent Publication 47-6420 public affairs The polymerization etc. recorded in report, Japanese Patent Publication 47-10059 bulletin obtains polyoxymethylene homopolymer.Herein, formaldehyde is excellent Choosing is without containing impurity such as water, methanol.
As polymerization catalyst, it is not particularly limited as long as anionic polymerization catalytic agent, for example,Salt is birdsed of the same feather flock together Catalyst etc. is closed, specifically, for substance represented by the following general formula (2).
[R3 R4 R5 R6 M]+×-···(2)
(in formula, R3、R4、R5、R6Alkyl is each independently represented, M indicates that the element with lone pair electrons, X indicate nucleophilic Property group.)
Represented by above-mentioned general formula (2), it is preferable to use tetraethyl iodate in salt polymerization catalystTributyl second Base iodateEqual seasonsThe quaternary ammonium compounds such as salt compounds, 4 bromide, dimethyl distearyl ammonium acetate. More preferably use dimethyl distearyl ammonium acetate.
The import volume of polymerization catalyst is preferably 0.0001 mole or more and 0.01 mole hereinafter, more relative to monomer 1kg Preferably 0.0005 mole or more and 0.005 mole hereinafter, further preferably 0.001 mole or more and 0.003 mole or less. When import volume is 0.0001 mole or more, polymerization speed becomes faster, and yield improves, and is economically preferred.Import volume rubs for 0.01 When you are following, polymerization system is easy to become uniformly, thus it is preferred that.
As molecular weight regulator, specifically, using alcohol, carboxylic acid anhydrides, carboxylic acid etc., preferably methanol, ethyl alcohol, propionic acid Acid anhydride, acetic anhydride, more preferably acetic anhydride.The import volume of molecular weight regulator relative to preferably 0.005 mole or more of monomer 1kg and 0.008 mole or less.
As hydrocarbon equal solvent, as long as to be not particularly limited as long as the compound reacted with formaldehyde, preferably pentane, isoamyl Alkane, hexane, hexamethylene, heptane, octane, nonane, decane, benzene etc..More preferably hexane.Alternatively, it is also possible to which two or more is mixed It uses.
As long as polyplant can supply simultaneously formaldehyde, molecular weight regulator,The device of salt polymerization catalyst is just It is not particularly limited, well known device can be used, can be batch-type, continous way etc..Preferably continuous polyplant.
The terminal groups of the polyoxymethylene homopolymer obtained in this way are largely hydroxyl, therefore thermally labile, can make end End stabilizes.
Chemically treated method is carried out to well known terminal groups as that can enumerate end stabilizing method.For example, phase For polymer 1kg, put into 0.1kg or more and 90kg or less chemical treatments, temperature be 140 DEG C or more and 150 DEG C or less, Time is to be chemically treated for 20 minutes or more and 100 minutes or less.Device can may be batch-type for continous way, preferably For continous way device.In addition, chemical treatments can be used the chemical treatments such as esterifying agent, etherifying agent, in present embodiment The chemical treatments of terminal groups are preferably esterifying agent.
In using method of the esterifying agent as chemical treatments, it can enumerate in No. 3459709 specifications of U.S. Patent No. Record using a large amount of acid anhydrides to be recorded in No. 3172736 specifications of method and U.S. Patent No. that slurry form carries out Use the gas of acid anhydrides method performed in the gas phase etc..
As esterifying agent, method, the using gas method performed in the gas phase carried out with slurry form it is any in, Organic acid anhydride represented by the following general formula (3), benzoyl oxide, succinic anhydride, maleic anhydride, glutaric anhydride, adjacent benzene two can be enumerated Formic anhydride etc..
R7 C O O C O R 8···(3)
(in formula, R7、R8Each independently represent alkyl.R7、R8It can be the same or different.)
In organic acid anhydride represented by above-mentioned general formula (3), preferably propionic andydride, acetic anhydride, more preferable acetic anhydride.Organic acid Acid anhydride, which can be used a kind, also can be used two or more.
As method of the etherifying agent as chemical treatments is used, there is the side recorded in Japanese Patent Publication 63-452 bulletin Method etc., as present embodiment it is end stabilizing used in etherifying agent, ortho esters can be enumerated, can usually enumerate aliphatic or Aromatic acid and aliphatic, alicyclic or aromatic alcohols ortho esters etc., specifically, original acid A ester or orthoformic acid can be enumerated Ethyl ester, ortho-acetic acid methyl esters or ethyl orthoacetate and former methyl benzoate or former ethyl benzoate, orthocarbonic ester, ethyl orthocarbonate Deng.
In etherification reaction, preferably with respect to etherifying agent 1kg import 0.001kg or more and 0.02kg or less p-methyl benzenesulfonic acid, The Lewis acid-types such as hardness inorganic acid are urged in strong organic acid, dimethyl suflfate, dithyl sulfate etc. in acetic acid, hydrobromic acid etc. Agent.
The preferred solvent of etherification reaction is the low boiling points aliphatic, alicyclic and aromatic series such as pentane, hexane, hexamethylene, benzene Hydrocarbon；The organic solvents such as the halogen-lowers aliphatic such as methylene chloride, chloroform, carbon tetrachloride.
The mode of polymerization is not particularly limited, and in order to be readily derived the powder of polyoxymethylene homopolymer, preferably becomes silted up Slurry polymerization, bulk polymerization.
[manufacturing method of polyacetals: polyoxymethylene copolymer]
By formaldehyde and/or metaformaldehyde and cyclic ether and/or cyclic formals or it is added with 1 mass ppm or more and 500 Have obtained from the copolymerization of the cyclic formals of quality ppm hindered phenol anti-oxidants below and is including Oxymethylene list Member-(CH2O)-chain in the substance of structure randomly inserted with oxygen alkylidene unit represented by the following general formula (1) be polyoxy Methylene base co-polymer.
(the R in formula1And R2Respectively hydrogen atom, alkyl or aryl, they can be the same or different, and n is 2~6 Integer)
Metaformaldehyde is the cyclic trimer of formaldehyde, for example, by making formalin in the presence of acidic catalysts Reactant aqueous solution and obtain.In the metaformaldehyde, the impurity of its chain tra nsfer is made containing water, methanol, formic acid, methyl formate etc., Therefore preferably these impurity are removed by the methods of distillation to purify.At this point, preferably with respect to 1 mole of metaformaldehyde by chain tra nsfer The total amount of impurity be adjusted to 1 × 10-3Mole hereinafter, more preferably 0.5 × 10-3Mole or less.1×10-3Mole or less When, polymerization rate will not be slack-off, the good thermal stability of the polymer of generation.
Cyclic ether and/or cyclic formals are the ingredients that can be copolymerized with metaformaldehyde, specifically, epoxy second can be enumerated Alkane, propylene oxide, epoxy butane, epichlorohydrin, epibromohydrin, styrene oxide, oxetanes, 1,3- dioxolane, second Glycol formal, propylene glycol, diethylene glycol formal, triethylene glycol, 1,4-butanediol formal, 1,5- penta Glycol formal, 1,6- hexanediol formal etc..In these cyclic ethers and/or cyclic formals, preferably 1,3- dioxane penta Alkane, 1,4-butanediol formal.
The additive amount of cyclic ether and/or cyclic formals is relative to 1 mole of metaformaldehyde preferably 1 mole of % or more and 20 Mole % hereinafter, more preferably 1 mole of % or more and 15 mole of % hereinafter, further preferably 1 mole of % or more and 10 rubbing That % is hereinafter, particularly preferably 1 mole of % or more and 5 mole of % or less.
As polymerization catalyst, preferred Lewis acids, Bronsted acid and the cationic active catalysts such as its ester or acid anhydride.As road Lewis acid, for example, the halide etc. of boron, tin, titanium, phosphorus, arsenic and antimony can be enumerated, specifically, boron trifluoride, four chlorinations can be enumerated Tin, titanium tetrachloride, phosphorus pentafluoride, phosphorus pentachloride, antimony pentafluoride and its complex compound or salt etc..In addition, as Bronsted acid, its ester or Acid anhydride, specifically, can enumerate perchloric acid, trifluoromethanesulfonic acid, heteropoly acid, isopolyacid, the perchloric acid tert-butyl ester, acetylperchlorate, Trimethyl oxygenHexafluorophosphoric acid ester etc..Among them, preferably boron trifluoride, boron trifluoride hydrate；It is former containing oxygen atom or sulphur The organic compound of son and the co-ordination complex of boron trifluoride, specifically, boron trifluoride two can be enumerated as preferred example Ethylether, boron trifluoride di-n-butyl ether.The usage amount of these polymerization catalysts is relative to formaldehyde and/or metaformaldehyde and ring-type 1 mole preferably 1 × 10 of total amount of ether and/or cyclic formals-6Mole or more and 1 × 10-3Mole hereinafter, more preferable 5 × 10-6Mole or more and 1 × 10-4Mole or less.
From the aspect of equably being reacted, preferably with not causing dysgenic atent solvent dilute polymerization reaction It releases above-mentioned catalyst used in present embodiment and is added into monomer.As the solvent of catalyst dilution, as long as not The organic solvent for participating in polymerization reaction can just use.It is, for example, possible to use the aromatic hydrocarbon such as benzene,toluene,xylene；Just oneself The aliphatic hydrocarbons such as alkane, normal heptane, hexamethylene；The halogenated hydrocarbons such as chloroform, methylene chloride；Ether, diethylene glycol dimethyl ether, Isosorbide-5-Nitrae-dioxy Ethers such as azacyclohexane etc..Moisture regulation is preferably specific range by these solvents, can sufficiently remove water by zeolite etc. It is used after point.
It, can be using any in slurry method, substance law, fusion method etc. as the polymerization of polyoxymethylene copolymer Kind.In addition, the shape (structure) of the polymerization machine used is it is not also specifically limited, it is preferred that thermal medium can circulate in the jacket The paddle of twin-screw, screw be stirred type polyplant.As used in continuous bulk polymerization Polyplant, the continuous extruder and mixing roll of co-kneader, double-screw type, twin-screw paddle type continuous mixer etc. can be used from clear Up to the present the continuous polymerization unit of the metaformaldehydes proposed such as clean type extrusion mixing machine etc..The temperature of polymerization machine is preferred 63 DEG C or more and 135 DEG C are maintained at hereinafter, more preferably 70 DEG C or more and 120 DEG C of ranges below, further preferably 70 DEG C Above and 100 DEG C of ranges below.Delay (reaction) time in polymerization machine be preferably 0.1 minute or more and 30 minutes with Under, more preferably 0.1 minute or more and 25 minutes hereinafter, further preferably 0.1 minute or more and 20 minutes or less.If polymerization The temperature of reaction machine and residence time are above-mentioned range, then with the tendency of continual and steady polymerization reaction.
The inactivation of the polymerization catalyst contained in the polyoxymethylene copolymer as obtained from polymerization reaction can pass through Investment contains the amines such as ammonia, triethylamine, tri-n-butylamine；Boronic acid compounds class；It is the hydroxide of alkali or alkaline earth metal, inorganic In the catalyst such as hydrochlorate, acylate and in the aqueous solution and/or organic solvent of deactivator, several points are usually stirred with slurry form Clock~a few hours carry out.At this point, first being crushed after preferred polymeric and being carried out afterwards when polyoxymethylene copolymer is big bulk Processing.Later, it is carried out by filtration drying.
As in catalyst and deactivator, it can be used alone quaternary ammonium compound or can also be lost with above-mentioned catalyst Agent living is used in combination, due to can be more effectively carried out the neutralization of catalyst and it is preferred that.In addition, being not particularly limited, preferably by making The steam of ammonia, triethylamine etc. contacts with polyoxymethylene copolymer and makes the method for catalyst inactivation, by making hindered amines, three At least one kind of and polyoxymethylene copolymer of Phenylphosphine, calcium hydroxide, boronic acid compounds or quaternary ammonium compound etc. is in mixing machine The method for contacting and making catalyst inactivation.
Due in the polyoxymethylene copolymer after polymerization catalyst inactivates there are the end section of thermally labile, The decomposition for implementing unstable end section is removed and is stabilized.
It, will in the presence of alkaline matter for example, can enumerate as the method for decomposing and removing of unstable end section The side of at least process of two steps of process and the process for removing the Form aldehyde release generated by decomposition that polymer melting is kneaded Method.As device, it is preferable to use can continuously implement the single screw extruder with gas vent, the band of the process of above-mentioned two step The double screw extruder etc. of gas vent.As above-mentioned alkaline matter, the amines such as ammonia, triethylamine, tri-n-butylamine can be enumerated；Hydrogen-oxygen Change hydroxide, inorganic acid salt, the acylate of the alkali or alkaline earth metals such as calcium；Quaternary ammonium compound etc..Due to minute quantity The additive amount available polyoxymethylene copolymer for hardly remaining unstable end section in a very short period of time, therefore it is special It is preferable to use quaternary ammonium compounds shown in following formula (4).In addition, above-mentioned alkaline matter can be used together with water, methanol, The alkaline matter that two or more kinds may be used.
[R9 R10 R11 R12 N+]mX-m···(4)
(in formula, R9、R10、R11、R12It each independently represents the unsubstituted alkyl of carbon atom number 1~30 or replaces alkyl； The aryl of carbon atom number 6~20；The unsubstituted alkyl of carbon atom number 1~30 replaces alkyl by least one carbon atom number 6~20 Aryl replace after aralkyl；The aryl of carbon atom number 6~20 by the unsubstituted alkyl of at least one carbon atom number 1~30 or Alkylaryl after replacing alkyl to replace, unsubstituted alkyl or substitution alkyl are straight chain, branch or ring-type.Above-mentioned substitution alkyl Substituent group is halogen, hydroxyl, aldehyde radical, carboxyl, amino or amide groups.In addition, above-mentioned unsubstituted alkyl, aryl, aralkyl, alkyl The hydrogen atom of aryl can be optionally substituted by halogen.M indicates 1~3 integer.X indicates carboxylic acid, the halogen of hydroxyl or carbon atom number 1~20 Change the sour residue of organic thio-acid containing hydracid, oxyacid, inorganic thio-acid or carbon atom number 1~20 other than hydrogen.)
As quaternary ammonium compound, substance represented by preferably above-mentioned formula (4), the R in above-mentioned formula (4)9、R10、R11、R12Respectively From the hydroxy alkyl for the alkyl or carbon atom number 2~4 for being independently more preferably carbon atom number 1~5, wherein R9、R10、R11、R12 At least one be more preferably hydroxyethyl.Specifically, tetramethyl-ammonium, tetraethyl ammonium, tetrapropyl ammonium, four can be enumerated just Butyl ammonium, cetyltrimethylammonium ammonium, ammonium, 1,6- hexamethylene bis (trimethyl ammonium), decamethylene bis- (three Methyl ammonium), trimethyl -3- chlorine-2-hydroxyl propyl ammonium, trimethyl (2- hydroxyethyl) ammonium, triethyl group (2- hydroxyethyl) ammonium, three Propyl (2- hydroxyethyl) ammonium, three normal-butyls (2- hydroxyethyl) ammonium, tri methyl benzyl ammonium, triethylbenzyl ammonium, tripropyl benzyl Base ammonium, three normal-butyl hexadecyldimethyl benzyl ammoniums, trimethylphenyl ammonium, triethyl group phenyl ammonium, trimethyl -2- oxygen ethyl ammonium, three hydroxyl second of monomethyl Base ammonium, Dan Yiji trihydroxyethyl ammonium, octadecyl three (2- hydroxyethyl) ammonium, four (hydroxyethyl) ammoniums etc., hydroxide；Salt Acid, hydrobromic acid, hydrofluoric acid etc. contain hydrohalogenic acid salt；Sulfuric acid, nitric acid, phosphoric acid, carbonic acid, boric acid, chloric acid, acid iodide, silicic acid, perchloric acid, Asia The oxysalt of chloric acid, hypochlorous acid, chlorosulfonic acid, sulfamic acid, two sulfuric acid, tripolyphosphate etc.；The thiosalts such as thiosulfuric acid；First Carboxylates such as acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, octanoic acid, capric acid, benzoic acid, oxalic acid etc..Wherein, preferably Hydroxide (OH-), sulfate (HSO4-、SO4 2-), carbonate (HCO3 -、CO3 2-), borate (B (OH)4-), carboxylate.These In carboxylic acid, more preferable formic acid, acetic acid, propionic acid.These quaternary ammonium compounds may be used singly or in combination of two or more. In addition, amines such as ammonia, triethylamine etc. can be used together other than above-mentioned quaternary ammonium compound.
The additive amount of quaternary ammonium compound is converted into represented by following mathematical expressions (5) relative to polyoxymethylene copolymer The amount of nitrogen from quaternary ammonium compound, preferably 0.05 mass ppm or more and 50 mass ppm or less.
P×14/Q···(5)
(in formula, P indicates concentration (quality ppm) of the quaternary ammonium compound relative to polyoxymethylene copolymer, and 14 be the original of nitrogen Son amount, Q indicate the molecular weight of quaternary ammonium compound.)
When the additive amount of quaternary ammonium compound is 0.05 mass ppm or more, the decomposition removal rate of unstable terminal part will not It reduces, when being 50 mass ppm or less, the tone of the polyoxymethylene copolymer after the decomposition removing of unstable terminal part will not be bad Change.The adding method of quaternary ammonium compound is not particularly limited, and has the shape in the process for inactivating polymerization catalyst with aqueous solution Method, the method being blown to the oxymethylene copolymer before melting, the method added after melting that formula is added etc., however, making With any adding method, as long as polymer exists in the process of melt process.
By applying aforementioned stable method, unstable terminal part is considerably less and thermostabilization is excellent, can with the short time and It easily obtains weather stain and is detained the polyoxymethylene copolymer of coloring improvement.
The mode of polymerization is not particularly limited, and in order to be readily derived the powder of polyoxymethylene copolymer, preferably becomes silted up Slurry polymerization, bulk polymerization.
<polyacetals particle>
As long as the polyacetals particle of present embodiment makes the shape of the polyacetals obtained by above-mentioned manufacturing method Grain is just not particularly limited for graininess, for example, by the way that polyacetals obtained in extruder to be discharged from the die section of extruder, It is cooled down the methods of by water-bath cooling to obtain after earnestly.In addition, can be granulated after cooling to be granulated.It can lead to Cross the size or shape of die section, size, the shape of particle that earnestly etc. suitable controls obtain.
<size of particle>
The longest diameter (also referred to as major diameter) of polyacetals particle be preferably 5mm hereinafter, more preferably 2mm or more and 5mm with Under.It is 5mm polyacetals particle below by using major diameter, the polyacetals particle containing foreign matter can be greatly decreased.In addition, bunching The most short diameter (minor axis) of aldehyde particle is preferably 4mm hereinafter, more preferably 1mm or more and 4mm are hereinafter, further preferably 1mm Above and 3mm or less.It is 4mm polyacetals particle below, 2 or more the polyacetals on aftermentioned access by using minor axis The case where grain overlapping, tails off, and the precision of grain sorting is got higher.In addition, on aftermentioned access, the preferred minor axis of polyacetals particle For the diameter that the height of polyacetals particle, the major diameter of polyacetals particle are with the highly orthogonal of polyacetals particle.
<shape of particle>
The shape of polyacetals particle is not particularly limited as long as graininess, can enumerate the shapes such as oblate spheroid, cylinder, It is preferred that oblate spheroid.By the way that for oblate spheroid, particle is easy arrangement without being overlapped, there is the tendency that can effectively sort.
<amount of formaldehyde>
The amount for the formaldehyde that the polyacetals particle of present embodiment is generated by 100 DEG C of heating be 10 mass ppm hereinafter, Preferably 8 mass ppm are hereinafter, more preferably 5 mass ppm or less.The amount of the formaldehyde generated by 100 DEG C of heating is 10 matter Amount ppm easily and efficiently removes foreign matter hereinafter, thus paraformaldehyde is not easy to be precipitated after long-term operating.Embodiment can be passed through The amount for the formaldehyde of the method measurement polyacetals particle of middle record generated by 100 DEG C of heating.
The amount for the formaldehyde that the polyacetals particle of present embodiment is generated by 120 DEG C of heating is preferably 10 mass ppm Hereinafter, more preferably 8 mass ppm are hereinafter, further preferably 5 mass ppm or less.The first generated by 120 DEG C of heating The amount of aldehyde be 10 mass ppm hereinafter, it is possible thereby to by after polyacetals particle drying use when drying temperature be set to it is higher simultaneously It will be set to shorter, the more difficult precipitation of paraformaldehyde after long-term operating drying time, it is easy more effectively to remove foreign matter.It can be with The amount for the formaldehyde of polyacetals particle generated by 120 DEG C of heating is measured by the method recorded in embodiment.
<foreign matter>
From blocking, bad, die failure the sight of molding for inhibiting mold for forming when carrying out microfabrication, shaping thin wall Point, inhibition are formed from the viewpoint of the defect after film, piece, and the polyacetals particle of present embodiment preferably comprises the particle of foreign matter It is few, even if containing foreign matter, it is also preferred that the size of foreign matter is small, quantity is few.Foreign matter is not particularly limited, and can enumerate by the poly- of polyacetals Close reaction obtain by-product, additive, the substance from carbide, since what certain reason was carried secretly out of system carrys out self-structure The metallic foreign body etc. of object.When foreign matter is the substance from carbide, foreign matter is easy to issue black, contains in aftermentioned sorting process There is the precision of the sorting of the particle of foreign matter high.
As long as foreign matter in present embodiment has from the appearance of polyacetals particle identifiable degree by visual observation Color, size, are not particularly limited.For example, the polyacetals of principal component is transparent substance, in contrast, wherein containing Foreign matters penetrate light, thus it is confirmed that.The foreign matter contained in the polyacetals particle obtained after aftermentioned sorting process Preferably smaller than 1.0mm, more preferably less than 0.3mm.
The content for the foreign matter that maximum width in polyacetals particle is 1.0mm or more is preferably 20/kg hereinafter, more preferably For 15/kg hereinafter, further preferably 0/kg.
Maximum width is that the number of the foreign matter of 1.0mm or more can with 11 by visual observation confirm the polyacetals of 3kg Grain temporarily collects the particle containing foreign matter, makes the grain dissolution with solvent, collect undissolved foreign matter, and surveyed with vernier caliper Scale cun.
Maximum width is that the foreign matter of 0.3mm or more is preferably 20/kg hereinafter, more preferably up to width is 0.3mm or more Foreign matter be 15/kg hereinafter, further preferably 0/kg.
The number for the foreign matter that maximum width is 0.3mm or more can be measured by following method etc..Make the bunching of 3kg Aldehyde grain dissolution settles foreign matter in hexafluoroisopropanol, by centrifugal separator, exhaust supernatant, again in hexafluoroisopropanol Disperse foreign matter, settles foreign matter by centrifugal separator.Repeatedly after the operation, separated by using the suction filtration of molecular filter Foreign matter.After foreign matter after separation is dried, 300 μm of screen size of sieve is crossed, and calculates every list of unsanctioned foreign matter The number of position quality.
<granulating working procedure>
As long as the granulating working procedure of present embodiment by it is above-mentioned as polymerization obtained from polyacetals be granulated for graininess, The amount of the formaldehyde generated by 100 DEG C of heating is 10 mass ppm hereinafter, being just not particularly limited.
<particle-size distributor>
As the particle-size distributor of present embodiment, without special as long as having the function of sorting the particle containing foreign matter Limitation, it is, for example, possible to use the particles with the composition for reaching above-mentioned function by the defined access configured by particle Sorting machine.Specifically, can enumerate Kubota Corp.'s Foreign substance separator, Satake Corp's light sorting machine, TECMAN Industrial Co., Ltd color selector etc..
<sorting process>
As long as the sorting process of present embodiment is to sort polyacetals particle by particle-size distributor, relative to whole bunchings The amount that the amount of aldehyde particle contains the polyacetals particle of foreign matter is the process less than 600 mass ppm, is just not particularly limited.For example, Polyacetals particle can be made by above-mentioned particle-size distributor, particle separation when coloured foreign matter is will test out, only collect not Particle etc. containing coloured foreign matter.Amount preferably with respect to the polyacetals particle that the amount of whole polyacetals particles contains foreign matter is 300 mass ppm or less.
Sorting process can be using all or part of of the polyacetals particle removed by particle-size distributor as granulation work The polyacetals of sequence recycles.It is preferred from the viewpoint of the effective use of material.
As the supply method of the polyacetals particle to particle-size distributor, although depending on the structure of particle-size distributor, The particle-size distributor that can for example enumerate using having defined access and the access to have grain sorting function, the access from Top supplies polyacetals, after grain sorting, falls Particle free, method thus separated etc..For access, from excellent It selects from the viewpoint of 11 in such a way that polyacetals particle is not laminated arranging, preferably the access of belt conveyor shape.2 When the above coincidence, it is possible to cannot fully play grain sorting function.It is therefore preferable that having 2 or more particles on access Sorting function.Once the access for having other grain sorting functions is further made it through, thus may be used after sorting particle as a result, To manufacture the polyacetals particle of high-purity.
It is not particularly limited to the feed speed of the polyacetals particle of particle-size distributor, it is excellent from the viewpoint of productivity It is selected as 1000kg/ hours or more, more preferably 2000kg/ hours or more, further preferably 3000kg/ hours or more.
Embodiment
Hereinafter, specific embodiment is enumerated and comparative example explains present embodiment in detail, as long as but present embodiment Without departing from its main idea, with regard to embodiment not limited to the following.In addition, the measuring method of the various characteristics in embodiment described below.
(1) measurement of the foreign matter in polyacetals particle
For polyacetals particle 3kg, the particle containing foreign matter is sorted by visual observation, then every 1 with vernier caliper measurement The size of the foreign matter contained in the particle containing foreign matter of grain.Then, it by measuring the total weight of the particle containing foreign matter, calculates Quality ppm containing foreign particles out.Then, particle 100g is suppressed 5 minutes under the pressure of 10MPa at 200 DEG C, is made 10 30cm × 30cm × about 1.2mm matrix band, and confirmed by visual observation.
There is the case where foreign matter of 1.0mm or more, be determined as ×
There is no the foreign matter of 1.0mm or more, have the case where foreign matter of 0.3mm or more, is determined as △
When not having the foreign matter of 0.3mm or more, having the foreign matter less than 0.3mm, number is counted, adds up to 30 or more feelings Condition is determined as zero
In addition to this case where, is determined as ◎.
(2) evaluation of lock out operation
It sorts in process, it is very high that every 1 hour lock out operation that can be carried out 3000kg or more is considered as lock out operation, comments Valence is ◎.
Lock out operation by can be carried out 1000kg or more for every 1 hour and less than 3000kg is considered as lock out operation height, evaluation It is zero.
It is low that the lock out operation that can only carry out less than 1000kg for every 1 hour is considered as lock out operation, be evaluated as ×.
The case where run stability is gone wrong is evaluated as △.
(3) formaldehyde in polyacetals particle
The amount of the formaldehyde generated by the heating of 100 DEG C or 120 DEG C is measured as follows.In the Tedlar (registration with valve Trade mark) 20.00g polyacetals particle is packed into bag, after sufficiently carrying out nitrogen displacement, enclosed in Tedlar (registered trademark) bag 5.00L nitrogen.Later, on internal top, Tedlar (registrar is put into the baking oven of the sample tap of outside perforation having Mark) bag and connect sampling bag, then 100 DEG C or 120 DEG C at a temperature of place 1 hour.Later, in sample tap connection DNPH filter Core opens the valve of sampling bag, and 4.00L gas is made to pass through DNPH filter core.The acetonitrile of 5mL is set to pass through DNPH filter core with constant speed, Formaldehyde is recovered in 10mL measuring bottle.Water is added later to 10mL, is sufficiently mixed.The liquid dispensing of the mixing is entered into sampling bottle, is made With Shimadzu Seisakusho Ltd. HPLC, titer uses DNPH titer, and separating liquid uses water/acetonitrile (52/48), with flow 1mL/ points Clock, 40 DEG C of column temperature quantified, the formaldehyde that every granular mass generates is determined with ppm.Determination of the upper limit is 15ppm hereinafter, will surpass The case where crossing determination of the upper limit is denoted as O.D..
(4) size of polyacetals particle
For the maximum diameter and minimum diameter of polyacetals particle, 100 polyacetals particles are measured using vernier caliper, are led to It crosses average and finds out.
[Production Example of polyacetals particle]
(POM-1)
The polymerization machine of the twin-screw self-cleaning type of the jacketed for the thermal medium that can circulate is adjusted to 80 DEG C, it is small with 12kg/ When continuously add metaformaldehyde, with 414.6g/ hours (relative to 1 mole of metaformaldehyde be 4.2 moles of %) continuously add It was continuously added using 6.8g/ hours as chain as 1, the 3- dioxolane of comonomer, relative to 1 mole of metaformaldehyde The dimethoxym ethane of transfer agent.In addition, continuously adding the 1 mass %'s of boron trifluoride di-n-butyl etherate as polymerization catalyst Cyclohexane solution 38g/ hours, and polymerize.The mode of polymerization is bulk polymerization.The polyacetals being discharged by polymerization machine is copolymerized The inactivation of polymerization catalyst is carried out in powder investment 0.1% aqueous solution of triethylamine of object.After being filtered with centrifugal separator inactivation Copolyacetal, in 140 DEG C of dryings after cleaning, to obtain thick polyacetals.
Later, addition containing as quaternary ammonium compound trimethyl -2- hydroxyethyl ammonium formate 1 mass parts of aqueous solution, Triethylene glycol bis- [3- (3- tert-butyl -5- methyl -4- hydroxy phenyl) propionic ester] 0.3 mass parts, tristearin as antioxidant Sour 0.2 mass parts of calcium, to the double-screw type extruder supply with gas vent.5 weights are added to the polyacetals melted in an extruder 2 mass parts of % triethylamine aqueous solution are measured, the set temperature of extruder is set as 200 DEG C, carries out the decomposition of unstable terminal part. Then, the polyacetals devolatilization after decomposing unstable terminal part under conditions of gas vent 20 support of vacuum degree, by extruder Die section discharge.By the polyacetals being discharged from die section earnestly after water-bath cooling, to obtain polyacetals particle.
In extrusion, operated under conditions of the revolving speed of screw rod is 100rpm, after operation start 10 hours POM-1 Manufacture change revolving speed suitably as 50rpm, 100rpm, 150rpm, thus adjust in polyacetals particle contain it is different The grain amount of object.The amount of the obtained particle containing foreign matter in polyacetals particle is 1200ppm, wherein containing with 1mm The foreign matter of above size.
(POM-2)
By the strands water-bath cooling for the polyacetals being discharged from die section, be then granulated, in addition to this, by with POM-1 The same method of manufacturing method obtained polyacetals particle.The amount of the obtained particle containing foreign matter in polyacetals particle is 1200ppm, in the foreign matter wherein containing the size with 1mm or more.
(POM-3)
Quaternary ammonium compound is not added in obtained thick polyacetals, adds 2,2- di-2-ethylhexylphosphine oxide (4- methyl-t-butyl benzene Phenol) 0.3 mass parts replace triethylene glycol it is double-[3- (3- tert-butyl -5- methyl -4- hydroxy phenyl) propionic ester] as anti-oxidant Agent has obtained polyacetals particle by method same as the manufacturing method of POM-1 in addition to this.Obtained polyacetals particle In the particle containing foreign matter amount be 1200ppm, wherein containing with 1mm or more size foreign matter.
[particle-size distributor]
In aftermentioned embodiment and comparative example, the Foreign substance separator of Satake Corp: product name has been used PCS600BFD type.
(embodiment 1)
Lock out operation is carried out using Foreign substance separator to POM-1, passes through it with about 1000kg/ hours speed.
On the access for having particle-size distributor, particle is arranged in a manner of nonoverlapping.It can with all-the-time stable handle Grain.Result is shown in table 1.
(embodiment 2~4)
Other than the condition shown in the table 1, implement similarly to Example 1.Result is shown in table 1.
(embodiment 5)
For POM-2, lock out operation is carried out using Foreign substance separator, passes through it with about 1000kg/ hours speed.? Result is shown in table 1.
(embodiment 6~8)
Other than the condition shown in the table 1, implement similarly to Example 5.Result is shown in table 1.
(comparative example 1)
Lock out operation has been carried out by visual observation to the particle 3kg of POM-1.Time needs 1 hour.Result is shown in table 2.
(comparative example 2)
Lock out operation has been carried out by visual observation to the particle 3kg of POM-2.Time needs 1 hour.Result is shown in table 2.
(comparative example 3)
Other than using POM-3, lock out operation similarly to Example 1 has been carried out.Result is shown in table 2.
(comparative example 4)
The polymerization machine of twin-screw self-cleaning type with the thermal medium that can circulate is adjusted to 80 DEG C, with 12kg/ hours companies Add continuously metaformaldehyde, using 414.6g/ hours (relative to 1 mole of metaformaldehyde be 4.2 moles of %) continuously add as 1, the 3- dioxolane of comonomer was continuously added using 6.8g/ hours as chain tra nsfer relative to 1 mole of metaformaldehyde The dimethoxym ethane of agent.In addition, being continuously added to the ring of the 1 mass % of boron trifluoride di-n-butyl etherate as polymerization catalyst Hexane solution 38g/ hours is simultaneously polymerize.The mode of polymerization is bulk polymerization.The Copolyacetal that will be discharged by polymerization machine Powder investment 0.1% aqueous solution of triethylamine in and carry out the inactivation of polymerization catalyst.It is filtered with centrifugal separator the poly- of inactivation Acetal copolymer, in 140 DEG C of dryings after cleaning, to obtain thick polyacetals.
Later, addition containing as quaternary ammonium compound trimethyl -2- hydroxyethyl ammonium formate 1 mass parts of aqueous solution, As 2,2- di-2-ethylhexylphosphine oxide (4- methyl-t-butyl phenol) 0.3 mass parts of antioxidant, 0.2 mass parts of calcium stearate and to The double-screw type extruder supply for having sieve (#200 mesh) on porous plate with gas vent.It is poly- to what is melted in an extruder 5 weight % triethylamine aqueous solution, 2 mass parts are added in acetal, and the set temperature of extruder is set as 200 DEG C, has carried out shakiness Determine the decomposition of terminal part.Then, the polyacetals after decomposing unstable terminal part under conditions of gas vent 20 support of vacuum degree takes off Volatile matter, and be discharged by extruder die head.By the polyacetals being discharged from die section earnestly after water-bath cooling, to obtain bunching Aldehyde particle.
In extrusion, operated under conditions of the revolving speed of screw rod is 100rpm, after operation start 10 hours acquire it is poly- Acetal particle changes revolving speed suitably for 50rpm, 100rpm, 150rpm.Result is shown in table 2.
(comparative example 5)
Other than changing fervent speed, changing the size of particle, implement in the same manner as the manufacturing method of POM-1.? Result is shown in table 2.
As shown in table 1, in Examples 1 to 8, the grain amount containing foreign matter is 600ppm hereinafter, it may thus be appreciated that it is high-quality. In addition, can be with 1000kg/ hours progress lock out operation, therefore can effectively obtain polyacetals particle.
In the comparative example 1 and 2 for carrying out foreign matter sorting by visual observation without using particle-size distributor, available polyacetals The few polyacetals particle of particle containing foreign matter in grain, but practical good lock out operation cannot be obtained.
In comparative example 3, the thermal stability of polyacetals particle is low, therefore speculates it is the influence because of the formaldehyde generated, cannot Lock out operation is carried out well.
Comparative example 4 and 5 does not carry out lock out operation, therefore particle largely containing foreign matter is mixed into polyacetals particle.
[table 1]
[table 2]
Industrial applicability
The manufacturing method of polyacetals particle of the invention is in electric and electronic Material Field, automotive field, various other works Small formed product material, the food used in various parts material, film/sheet material, machinery or device in industry Material Field etc. There is industrial applicability in the fields such as the packaging material of product.

Claims (7)

1. a kind of manufacturing method of polyacetals particle comprising following process:
Granulating working procedure, the amount as obtaining the formaldehyde generated by 100 DEG C of heating by polyacetals obtained from polymerization are 10 Quality ppm polyacetals particle below；With
Process is sorted, the polyacetals particle is sorted using particle-size distributor, to obtain relative to whole polyacetals The amount that the amount of particle contains the polyacetals particle of foreign matter is less than the polyacetals particle of 600 mass ppm,
Wherein, the shape of the polyacetals particle is oblate spheroid, and the longest diameter of the polyacetals particle is 5mm hereinafter, described The most short diameter of polyacetals particle is 3mm hereinafter, the particle-size distributor is selected from Foreign substance separator, light sorting machine and color selector.
2. the manufacturing method of polyacetals particle as described in claim 1, wherein the foreign matter is from the different of carbide Object.
3. the manufacturing method of polyacetals particle as claimed in claim 1 or 2, wherein the foreign matter is less than 1.0mm.
4. the manufacturing method of polyacetals particle as claimed in claim 1 or 2, wherein the sorting process is will be described in All or part of sorting recycled as the polyacetals of the granulating working procedure for the polyacetals particle that particle-size distributor removes Process.
5. the manufacturing method of polyacetals particle as claimed in claim 1 or 2, wherein the foreign matter is less than 0.3mm,
The sorting process is that obtain relative to the amount of the polyacetals particle described in polyacetals particle total amount containing foreign matter be 300 matter Measure the sorting process of ppm polyacetals particle below.
6. the manufacturing method of polyacetals particle as claimed in claim 1 or 2, wherein the granulating working procedure is to obtain by 120 DEG C heating and the amount of formaldehyde that generates be 10 mass ppm polyacetals below polyacetals particle granulating working procedure.
7. a kind of polyacetals particle, is obtained by manufacturing method of any of claims 1 or 2.
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