CN102131865A - Polyacetal resin composition - Google Patents
Polyacetal resin composition Download PDFInfo
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- CN102131865A CN102131865A CN2008801308489A CN200880130848A CN102131865A CN 102131865 A CN102131865 A CN 102131865A CN 2008801308489 A CN2008801308489 A CN 2008801308489A CN 200880130848 A CN200880130848 A CN 200880130848A CN 102131865 A CN102131865 A CN 102131865A
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09J159/00—Adhesives based on polyacetals; Adhesives based on derivatives of polyacetals
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Abstract
Disclosed is a polyacetal resin composition containing a glass inorganic filler, which improves adhesion between the glass inorganic filler and a polyacetal resin, thereby obtaining excellent mechanical strength and hot water resistance. Specifically disclosed is a polyacetal resin composition obtained by blending 3-200 parts by weight of a glass inorganic filler (B) into 100 parts by weight of a polyacetal resin (A). Into this polyacetal resin composition, there is further blended 0.001-1.0 part by weight of a boric acid compound (C). The polyacetal resin component (A) is composed of 99.9-80 parts by weight of a polyacetal resin (A1) having 0-20 mmol/kg of hydroxy groups in a molecule, and 0.1-20 parts by weight of a modified polyacetal resin (A2) having 30-2000 mmol/kg of hydroxyl groups in a molecule.
Description
Technical field
The present invention relates to the polyacetal resin composite of mechanical characteristics and hot water resistance excellence.
Background technology
The known strongtheners such as category of glass inorganic filling material that cooperate for the mechanical characteristics, for example intensity or the rigidity that improve polyacetal resin.
But because polyacetal resin lacks activity, the category of glass inorganic filling material also lacks activity, both binding propertys are insufficient when only cooperating the category of glass inorganic filling material to carry out melting mixing in polyacetal resin, can not get more expect the raising of the mechanical characteristics of degree.
For hot water resistance also is similarly, and both binding propertys are insufficient when only cooperating the category of glass inorganic filling material to carry out melting mixing in polyacetal resin, as the characteristic after the hot-water cure, can not get the intensity maintenance effect that institute expects degree more.
Therefore, propose to be used to improve the binding property of polyacetal resin and category of glass inorganic filling material, thereby improved the whole bag of tricks of mechanical characteristics and hot water resistance.
For example, known category of glass inorganic filler and the boronic acid compounds of in polyacetal resin, adding, and then this category of glass inorganic filler is carried out surface treatment (with reference to Japanese kokai publication hei 9-151298 communique (with reference to claim 1 with specific silane compound, claim 4)), in polyacetal resin, add category of glass inorganic filling material and hydroxy carboxylic acid compound, and then this category of glass inorganic filling material is carried out surface treatment (with reference to TOHKEMY 2002-371168 communique (with reference to claim 1 with specific silane compound, claim 3)), in polyacetal resin, add the modified polyacetal resin (with reference to TOHKEMY 2004-359791 communique (claim 1)) that has the hydroxyl more than the 50mmol/kg in category of glass inorganic filling material and the molecule etc.
Summary of the invention
But, though these methods can improve the chemically reactive of category of glass inorganic filling material or increase active function groups in polyacetal resin matrix, but only like this, for the binding property of improving chemically inert polyacetal resin and category of glass inorganic filling material, realizing may not be abundant excellent physical strength and the hot water resistance.
The present invention addresses the above problem, and its purpose is, provides to satisfy the higher mechanical characteristics that requires along with the expansion that utilizes the field of polyacetal resin in recent years and the polyacetal resin composite of hot water resistance.
The inventor in view of the above problems, further investigate in order to obtain having the reinforcement polyacetal resin composite of excellent mechanical properties and hot water resistance, found that, by cooperating specific modified polyacetal resin and boronic acid compounds with specific ratios, can improve the problems referred to above significantly, thereby finish the present invention.
Promptly, the present invention relates to polyacetal resin composite, it is characterized in that, in polyacetal resin composition (A) 100 weight parts, cooperating in the polyacetal resin composite of category of glass inorganic filling material (B) 3～200 weight parts, further cooperate boronic acid compounds (C) 0.001～1.0 weight part, simultaneously, this polyacetal resin composition (A) is polyacetal resin (A1) 99.9～80 weight parts with the hydroxyl that has 0～20mmol/kg in the molecule, constitute with the ratio of modified polyacetal resin (A2) 0.1～20 weight part of the hydroxyl that has 30～2000mmol/kg in the molecule.
Embodiment
Below the present invention is carried out specific description.The invention is characterized in, in the polyacetal resin composite of having strengthened having cooperated the category of glass inorganic filling material, as polyacetal resin composition (A), and with having the modified polyacetal resin (A2) of the hydroxyl of 30～2000mmol/kg in the polyacetal resin (A1) of the hydroxyl that has 0～20mmol/kg in the molecule and the molecule, and be combined with boronic acid compounds (C).
The polyacetal resin that uses among the present invention (A1) is with oxygen methylene (CH
2O-) be the unitary macromolecular compound of primary structure, can also contain the multipolymer (comprising segmented copolymer) of a small amount of other structural units for the polyoxy methylene homopolymer or except the oxygen methylene.
Common homopolymer is by the homopolymerization of anhydrous formaldehyde, or general formula (CH
2O)
nThe cyclic trimer three of cyclic oligomer, the particularly formaldehyde of the formaldehyde of [wherein, n is the integer more than 3] expression
The polymerization of alkane prepares.Usually the end-blocking by polymkeric substance makes it stable to thermolysis.
Multipolymer is at about 85～99.9 moles of %-CH
2The number-average molecular weight that the group that disperses the following general formula of 15～0.1 moles of % to represent in the O-recurring group forms is the macromolecular compound more than 5000,
(in the formula, R
1And R
2Be selected from hydrogen atom, low alkyl group and junior alkyl halides respectively, in addition R
3Be selected from the methylene radical of methylene radical, oxygen methylene, low alkyl group and haloalkyl replacement and the oxygen methylene of low alkyl group and haloalkyl replacement, m is 0～3 integer, and the carbonatoms of each low alkyl group is 1～2).
Described multipolymer is usually by formaldehyde or with general formula (CH
2O)
nThe cyclic oligomer of formaldehyde of [wherein n is the integer more than 3] expression, for example three
Alkane prepares with the compound copolymerization that is selected from cyclic ether and the cyclic formals, removes terminal l fraction by hydrolysis usually and makes it stable to thermolysis.
And, in alleged the cyclic ether compound and cyclic formals compound, do not comprise the cyclic ether compound with hydroxyl, cyclic formals compound and their derivative herein with hydroxyl.
As cyclic ether compound that is used for copolymerization or cyclic formals compound, for example can use oxyethane, 1,3-dioxolane, Diethylene Glycol formal, 1,4-butyleneglycol formal etc.
In addition, except that mentioned component, can also and assign to regulate the molecular weight of resulting polymers usually with the one-tenth of regulating molecular weight.As the composition that is used to regulate molecular weight, can enumerate and can not form unstable terminal chain-transfer agent, that is, methylal, methoxy methyl acetal, dimethoxy methylal, trimethoxy methylal, oxygen methylene di-n-butyl ether etc. have in the compound of alkoxyl group more than a kind or 2 kinds.
In the preparation of known above-mentioned polyacetal resin in the past, because the effect of the moisture that the monomer component that uses in reaction, comonomer contain as impurity in becoming to grade, methyl alcohol etc. imports the hydroxyl that denier is arranged in the molecule of polyacetal resin.Therefore, in order to make the amount that imports to the hydroxyl in the molecule is 0～20mmol/kg, the total amount of total amount, methyl alcohol that is used for the moisture that polymeric composition (monomer component, comonomer become grade) contains is with respect to being used for polymeric composition total amount, must be respectively 30ppm following, preferably be respectively 20ppm following, be preferably below the 15ppm especially.
The polyacetal resin that uses among the present invention (A1) is that polyacetal (copolymerization) polymkeric substance of 0～20mmol/kg is object with the hydroxyl in the molecule of importing to of as above preparation, and the polyacetal resin of common industrial production belongs to this row.
Above-mentioned polyacetal resin (A1) as using among the present invention is preferably Copolyacetal, wherein is preferably three
Alkane be selected from the multipolymer that cyclic ether with hydroxyl and the compound copolymerization in the cyclic formals obtain.
Secondly, the modified polyacetal resin that uses among the present invention (A2) has 30～2000mmol/kg hydroxyl in molecule, preferably have the hydroxyl of 50～500mmol/kg.In addition, the number-average molecular weight of modified polyacetal resin (A2) is 1000～100000.
Quantitatively for example can being undertaken of the above-mentioned hydroxyl that polyacetal resin had by the method for putting down in writing in the TOHKEMY 2001-11143 communique.
Among the present invention, as with the modified polyacetal resin (A2) of above-mentioned polyacetal resin (A1) and usefulness, when using the few modified polyacetal resin of the import volume of hydroxyl, can not fully improve physical strength as the polyacetal resin composite that is combined with the category of glass inorganic filling material of the object of the invention.On the contrary, when using the excessive modified polyacetal resin of the import volume of hydroxyl, the thermostability of polyacetal resin composite etc. might be poor, and is therefore not preferred.
Among the present invention, above-mentioned modified polyacetal resin (A2) with hydroxyl can pass through prepared in various methods.
For example, can by have hydroxyl and bring into play the chain-transfer agent effect compound in the presence of, with three
Alkane be selected from the method for the compound copolymerization in cyclic ether and the cyclic formals, obtain the end of polymkeric substance has been given the modified polyacetal resin (A2) of hydroxyl.As the example of compound with hydroxyl, the compound that can enumerate the esterified compound of a hydroxyl part of polyalcohols, polyalcohols, polyalcohols or its ester addition oxyalkylene are obtained, water etc.As cyclic ether and cyclic formals, use the compound that does not have hydroxyl.
In addition, as other method, can also pass through three
Alkane, be selected from cyclic ether and compound in the cyclic formals with hydroxyl and method, obtain the side chain of polymkeric substance has been given the modified polyacetal resin (A2) of hydroxyl with polymerizable compound copolymerization of hydroxyl.
As above-mentioned polymerizable compound, can enumerate the cyclic formals class of hydroxyl, the glycidyl ethers of hydroxyl, the trimethylene oxide of hydroxyl, the styrenic of hydroxyl, the vinyl compound of hydroxyl etc.And; in aforesaid method; the hydroxyl that more preferably will have the polymerizable compound of hydroxyl is used suitable blocking group in advance, and for example with being used for polymerization after the protections such as acyl group such as formyl radical, ethanoyl or silyl, the protection of removing hydroxyl after the copolymerization forms the method for hydroxyl.Specifically, be with three
Alkane, the polymerizable compound copolymerization that is selected from the compound in cyclic ether and the cyclic formals and has protected hydroxyl; prepare the multipolymer that side chain has acyl group or silyl etc. thus; then; when side chain has acyl group with basic cpd, when side chain has silyl, this multipolymer is handled with acidic cpd; part or all that makes acyl group or silyl thus is decomposed to form hydroxyl, obtains the method for the required multipolymer with hydroxyl.
The modified polyacetal resin with hydroxyl (A2) that uses among the present invention can pass through method for preparing, but from the easiness of its molecular weight control, use the viewpoints such as thermostability of its polyacetal resin composite of the present invention to consider, the resin that preferably obtains not by the last method of utilizing chain-transfer agent to import hydroxyl, and preferably import the resin that the back method of hydroxyl obtains by the aftertreatment after copolymerization and the copolymerization carried out as required.As the polymerizable compound that is used for modification with hydroxyl, be preferably the cyclic formals class of hydroxyl, consider the further preferred Sericosol N that uses from the viewpoint of polymerization activity or importing rate.
In addition, as mentioned above, be preferably use especially and carry out copolymerization, and then carry out the method that aftertreatment obtains having the multipolymer of hydroxyl by the compound that acylated hydroxy or silanization with the cyclic formals of above-mentioned hydroxyl have carried out protection.As cyclic formals with protected hydroxyl, consider from the viewpoint of polymerization activity or hydroxyl importing rate, be preferably the Sericosol N acetic ester especially.
The modified polyacetal resin that uses among the present invention (A2) uses after can removing the l fraction that the polymer ends after the polymerization exists by hydrolysis, also can not be hydrolyzed to handle and directly use.
But; use has the polymerizable compound of protected hydroxyl; by copolymerization the side chain of polymkeric substance is given in the preparation of modified polyacetal resin (A2) of hydroxyl, must after the preparation of carrying out multipolymer by polymerization, be used the blocking group of the hydroxyl that basic cpd imports in to the polymeric pre-treatment to handle deprotection.
As the basic cpd that is used for the blocking group deprotection of hydroxyl, use amines such as ammonia, Trimethylamine, triethylamine, tributylamine, or the hydroxide salts of basic metal, alkaline-earth metal etc.
Among the present invention, constitute weight ratio A1/A2=99.9～80/0.1～20 of polyacetal resin (A1) with the modified polyacetal resin (A2) of polyacetal resin composition (A).
Modified polyacetal resin (A2) is less than 0.1 weight % or when surpassing 20 weight %, and the improvement of mechanical properties is all insufficient.Usually preferred ratio A 1/A2=99.5～90/0.5～10 of polyacetal resin (A1) and modified polyacetal resin (A2).
In addition, the present invention is the ratio that benchmark is adjusted A1/A2 with the modification degree (the importing rate of hydroxyl) of modified polyacetal resin (A2), the amount of hydroxyl groups that polyacetal resin (A1) is had preferably in order to show the raising of purpose physical strength effectively.
That is it is suitable increasing its mixture ratio when, using the low modified polyacetal resin (A2) of hydroxyl importing rate, reducing its mixture ratio when using the high modified polyacetal resin (A2) of hydroxyl importing rate.In addition, to reduce the mixture ratio of modified polyacetal resin (A2) for a long time be suitable to the amount of hydroxyl groups of polyacetal resin (A1) amount of hydroxyl groups that after a little while increases mixture ratio, the polyacetal resin (A1) of modified polyacetal resin (A2).
In addition, in polyacetal resin composite of the present invention, preferred polyacetal resin composition (A) contains a spot of polyacetal resin (A3) with branch or crosslinking structure, and mechanical characteristics or hot water resistance are more excellent thus.The ratio of polyacetal resin (A3) is preferably 0.01～3 weight part in polyacetal resin composition (A) 100 weight parts.When the ratio of polyacetal resin (A3) is very few, be difficult to stably show above-mentioned effect, variation such as formability in the time of too much.
Above-mentioned polyacetal resin (A3) with branch or crosslinking structure can be by in the preparation of above-mentioned polyacetal resin (A1), add and to have substituent monofunctional glycidyl base ether compounds such as alkyl, aryl, or multifunctional glycidyl ether such as butanediol diglycidyl ether carries out polymerization and prepares.
Secondly, as the category of glass inorganic filling material (B) that uses among the present invention, can enumerate the packing material of fibrous (glass fibre), granular (granulated glass sphere), Powdered (milled glass fiber), tabular (sheet glass) and hollow form (glass sphere), its particle diameter, staple length etc. are not limited especially, can use known any packing material.
Among the present invention, can from these packing materials, select a kind according to purpose and use or mix 2 kinds to use.
In addition, can also use undressed these category of glass inorganic filling materials among the present invention, but preferred the use implemented the inorganic filling material that surface treatment obtains by surface treatment agents such as silicane or titante coupling agents.
As silane coupling agent, for example can enumerate vinyl alkoxy silane, oxirane TMOS, aminoalkoxy silane, sulfydryl organoalkoxysilane, allyl group organoalkoxysilane etc.
As vinyl alkoxy silane, for example can enumerate vinyltriethoxysilane, vinyltrimethoxy silane, vinyl three ('beta '-methoxy oxyethyl group) silane etc.
As the oxirane TMOS, for example can enumerate γ-glycidoxypropyltrime,hoxysilane, β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, γ-glycidoxy propyl-triethoxysilicane etc.
As aminoalkoxy silane, for example can enumerate gamma-amino propyl trimethoxy silicane, γ-An Jibingjisanyiyangjiguiwan, gamma-amino propyl group methyl dimethoxysilane, gamma-amino propyl trimethoxy silicane, N-phenyl-gamma-amino propyl trimethoxy silicane etc.
As the sulfydryl organoalkoxysilane, for example can enumerate γ-Qiu Jibingjisanjiayangjiguiwan, γ-sulfydryl propyl-triethoxysilicane etc.
As the allyl group organoalkoxysilane, for example can enumerate γ-diallyl TSL 8330, γ-allyl amino propyl trimethoxy silicane, γ-allyl group sulfenyl (thio) propyl trimethoxy silicane etc.
In addition,, for example can enumerate isopropoxy ethohexadiol titanium, four titanium n-butoxide, four (2-ethyl hexyl oxy) titanium etc. as the titanate ester surface treatment agent.
The consumption of surface treatment agent is 0.01～20 weight part with respect to inorganic filling material 100 weight parts, is preferably 0.05～10 weight part, is preferably 0.05～5 weight part especially.
In addition, category of glass inorganic filling material (B) is under the situation of glass fibre, can further preferably use polymer binder, adhesion promoters, other auxiliary agent etc. as sizing agent (サ イ ズ agent).As the usually preferred material that uses organic class of polymer binder, material known in the past such as water dispersible/water miscible acetate polyvinyl ester, polyester, epoxide, urethane, polyacrylic ester, polyolefin resin or their mixture for example.
Among the present invention, the use level of category of glass inorganic filling material (B) is 3～200 weight parts with respect to polyacetal resin composition (A) 100 weight parts, is preferably 5～150 weight parts, is preferably 10～100 weight parts especially.The improvement of mechanical properties is insufficient during less than 3 weight parts, if surpass the then forming process difficulty that becomes of 200 weight parts.
Secondly,, ortho-boric acid, metaboric acid, tetraboric acid and boron trioxide can be enumerated, commercially available product can be used as the boronic acid compounds that uses among the present invention (C).The use level of boronic acid compounds (C) is 0.001～1.0 weight part with respect to polyacetal resin composition (A) 100 weight parts.
The boronic acid compounds that uses among the present invention (C), act on synergistically with the modified polyacetal resin (A2) that has the hydroxyl of 30～2000mmol/kg in formation, the particularly molecule of above-mentioned polyacetal resin composition (A), improve the binding property of polyacetal resin and category of glass inorganic filling material (B), can realize excellent physical strength and hot water resistance.The use level of boronic acid compounds (C) can not get required effect during less than 0.001 weight part, if surpass 1.0 weight parts then thermostability become problem.The use level of boronic acid compounds (C) is 0.005～0.5 weight part with respect to polyacetal resin composition (A) 100 weight parts preferably, is preferably 0.01～0.2 weight part especially.
In polyacetal resin composite of the present invention, can further cooperate known various stablizer, additive.As stablizer, can enumerate hindered phenol compound, nitrogenous compounds such as trimeric cyanamide, guanamines, hydrazides, urea, the oxyhydroxide of basic metal or alkaline-earth metal, inorganic salt, any more than a kind or 2 kinds in the carboxylate salt etc.In addition,, can enumerate the additive that usually in thermoplastic resin, uses as the additive that uses among the present invention, tinting material such as dyestuff, pigment for example, lubricant, nucleator, releasing agent, static inhibitor, in the tensio-active agent more than a kind or 2 kinds.
In addition, in the scope of the performance that can not reduce the object of the invention moulding product significantly, can also cooperate the weighting agent of fibrous, tabular, the powder shape etc. of known inorganic, organic and metal beyond a kind or the category of glass inorganic filling material of compound cooperation more than 2 kinds etc.As the example of this weighting agent, can enumerate talcum, mica, wollastonite, carbon fiber etc., but be not limited to these weighting agents.
Preparation of compositions method of the present invention is not limited especially, can be by easily preparing as normally used known equipment of existing resin combination preparation method and method.For example, can use following any method: after i) each composition being mixed, mixing and extrude preparation particle, the method for moulding then with forcing machine; Ii) different particles of forming of preparation earlier are used for moulding after then these particles being measured mixing in accordance with regulations, obtain the method for the moulding product that target forms after the moulding; Iii) with the method in the shaper etc. that directly joins more than a kind or 2 kinds of each composition.In addition, consider that from making these cooperation aspects, uniform component ground preferable methods is the part of resinous principle to be mixed the back with the form of fine powder add with other composition.
In addition, the resin combination that the present invention relates to can be by any one method moulding in extrusion moulding, injection molding, compressed moulding, vacuum forming, blow molding, the foaming.
Embodiment
Below, by embodiment the present invention is carried out more specific description, but the invention is not restricted to these embodiment.
[preparation of polyacetal resin (A1-1)]
To three
Alkane (moisture content 10ppm) 96mol% and 1, add methylal 1500ppm (with respect to whole monomers) in the mixture of 3-dioxolane (moisture content 10ppm) 4mol%, add the boron trifluoride (BF that causes catalyzer as reaction as molecular weight regulator
3) 20ppm (with respect to whole monomers) carries out polymerization.The polymkeric substance that obtains is imported in the aqueous solution that contains 0.05 weight % triethylamine, carries out the inactivation of catalyzer thus, so separate, washing, drying, thereby obtain rough polyacetal resin.
Then, with respect to rough polyacetal resin 100 weight parts that obtain, add the triethylamine 5 weight % aqueous solution 3 weight parts, trimeric cyanamide 0.15 weight part, [3-(3 for tetramethylolmethane base-four, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] (Irganox1010, チ バ ガ イ ギ one society's system) 0.3 weight part, with twin screw extruder at 200 ℃ of following melting mixings, carry out stabilization by removing of l fraction, obtain granular polyacetal resin with stablizer.The polyacetal resin that obtains is that melt index is that (MI) 27.0g/10min, number-average molecular weight are 41000, hydroxy radical content is the multipolymer of 5mmol/kg.
[preparation of polyacetal resin (A1-2)]
To three
Alkane (moisture content 10ppm) 96mol% and 1, add methylal 1030ppm (with respect to whole monomers) in the mixture of 3-dioxolane (moisture content 10ppm) 4mol%, add the boron trifluoride (BF that causes catalyzer as reaction as molecular weight regulator
3) 20ppm (with respect to whole monomers) carries out polymerization.The polymkeric substance that obtains is imported in the aqueous solution that contains 0.05 weight % triethylamine, carries out the inactivation of catalyzer thus, so separate, washing, drying, thereby obtain rough polyacetal resin.
Then, with respect to rough polyacetal resin 100 weight parts that obtain, add the triethylamine 5 weight % aqueous solution 3 weight parts, trimeric cyanamide 0.15 weight part, [3-(3 for tetramethylolmethane base-four, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] (Irganox1010, チ バ ガ イ ギ one society's system) 0.3 weight part, with twin screw extruder at 200 ℃ of following melting mixings, carry out stabilization by removing of l fraction, obtain granular polyacetal resin with stablizer.The polyacetal resin that obtains is that melt index is that (MI) 9.0g/10min, number-average molecular weight are 58000, hydroxy radical content is the multipolymer of 5mmol/kg.
[preparation of modified polyacetal resin (A2-1)]
To three
Alkane (moisture content 10ppm) 94mol%, 1, add methylal 50ppm (with respect to whole monomers) in the mixture of 3-dioxolane (moisture content 10ppm) 2mol% and Sericosol N acetic ester 4mol% (with respect to whole monomers), add the boron trifluoride (BF that causes catalyzer as reaction as molecular weight regulator
3) 20ppm (with respect to whole monomers) carries out polymerization.The polymkeric substance that obtains is imported in the aqueous solution that contains 0.05 weight % triethylamine, carries out the inactivation of catalyzer thus, so separate, washing, drying, thereby obtain rough polyacetal resin.Then; rough polyacetal resin 100 weight parts and 5 weight % triethylamine solution, 2000 weight parts that obtain are put in the reactor; 150 ℃ of following heat treated 1 hour, 170 ℃ of following heat treated 0.5 hour, carry out deacetylated with protected hydroxyl of removing of l fraction thus.It is 8: 1 mixing solutions that the triethylamine formulations prepared from solutions becomes the volumetric ratio of methyl alcohol and water.Further, the solution that will carry out heat treated is cooled to 20 ℃, obtains pulverous polyacetal resin thus.The number-average molecular weight of the modified polyacetal resin that obtains is 34500, has the hydroxyl of 100mmol/kg.
[preparation of modified polyacetal resin (A2-2)]
To three
Add methylal 50ppm (with respect to whole monomers) in the mixture of alkane (moisture content 10ppm) 92mol% and Sericosol N acetic ester 8mol% (with respect to whole monomers), add the boron trifluoride (BF that causes catalyzer as reaction as molecular weight regulator
3) 20ppm (with respect to whole monomers) carries out polymerization.The polymkeric substance that obtains is imported in the aqueous solution that contains 0.05 weight % triethylamine, carries out the inactivation of catalyzer thus, so separate, washing, drying, thereby obtain rough polyacetal resin.Then; rough polyacetal resin 100 weight parts and 5 weight % triethylamine solution, 2000 weight parts that obtain are put in the reactor; 150 ℃ of following heat treated 1 hour, 170 ℃ of following heat treated 0.5 hour, carry out deacetylated with protected hydroxyl of removing of l fraction thus.It is 8: 1 mixing solutions that the triethylamine formulations prepared from solutions becomes the volumetric ratio of methyl alcohol and water.Further, the solution that will carry out heat treated is cooled to 20 ℃, obtains pulverous polyacetal resin thus.The number-average molecular weight of the modified polyacetal resin that obtains is 72600, has the hydroxyl of 150mmol/kg.
[preparation of modified polyacetal resin (A2-3)]
To three
Alkane (moisture content 10ppm) 92mol% and 1 adds ethylene glycol 2800ppm (with respect to whole monomers) in the mixture of 3-dioxolane (moisture content 10ppm) 8mol%, add the boron trifluoride (BF that causes catalyzer as reaction
3) 50ppm (with respect to whole monomers) carries out polymerization.The polymkeric substance that obtains is imported in the aqueous solution that contains 0.05 weight % triethylamine, carries out the inactivation of catalyzer thus, so separate, washing, drying, thereby obtain rough polyacetal resin.Then; rough polyacetal resin 100 weight parts and 5 weight % triethylamine solution, 2000 weight parts that obtain are put in the reactor; 150 ℃ of following heat treated 1 hour, 170 ℃ of following heat treated 0.5 hour, carry out deacetylated with protected hydroxyl of removing of l fraction thus.It is 8: 1 mixing solutions that the triethylamine formulations prepared from solutions becomes the volumetric ratio of methyl alcohol and water.Further, the solution that will carry out heat treated is cooled to 20 ℃, obtains pulverous polyacetal resin thus.The number-average molecular weight of the modified polyacetal resin that obtains is 34600, has the hydroxyl of 50mmol/kg.
Embodiment 1～4, comparative example 1～2
Polyacetal resin (A1-1), modified polyacetal resin (A2-1 or A2-2 or A2-3), glass fibre (B-1), boronic acid compounds being pressed the ratio shown in the table 1 cooperate, is melting mixing in 200 ℃ the forcing machine at barrel temperature, prepares granular composition.Then, use injection moulding machine to be test film by granular composition molding, utilize evaluation method shown below to carry out evaluation of physical property.The result is as shown in table 1.
On the other hand,, situation of not adding modified polyacetal (A2) or the situation of not adding boronic acid compounds are prepared granular composition similarly, carry out evaluation of physical property for relatively.The result is as shown in table 1.
＜tensile strength and elongation 〉
To under the condition of 23 ℃ of temperature, humidity 50%, place 48 hours based on the tension test sheet of ISO3167, measure according to ISO527 then.
＜hot water resistance test 〉
To in 120 ℃ hot water, flood based on the tension test sheet of ISO3167 handled in 120 hours after, test film was placed 48 hours under the condition of 23 ℃ of temperature, humidity 50%, measure according to ISO527.Evaluation is 100% with the early strength of tensile strength, estimates with the conservation rate of tensile strength.
The category of glass inorganic filling material of＜use 〉
B-1: carried out the surface-treated glass fibre with isopropoxy ethohexadiol titanium
The boronic acid compounds of＜use 〉
C: ortho-boric acid
Embodiment 5～8, comparative example 3
Polyacetal resin (A1-2), modified polyacetal resin (A2-1 or A2-2 or A2-3), granulated glass sphere (B-2), boronic acid compounds being pressed the ratio shown in the table 2 cooperate, is melting mixing in 200 ℃ the forcing machine at barrel temperature, prepares granular composition.Then, use injection moulding machine to be test film by granular composition molding, utilize evaluation method shown below to carry out evaluation of physical property.The result is as shown in table 2.
On the other hand,, the situation of not adding modified polyacetal (A2) is prepared granular composition similarly, carry out evaluation of physical property for relatively.The result is as shown in table 2.
The category of glass inorganic filling material of＜use 〉
B-2: carried out the surface-treated granulated glass sphere with the gamma-amino propyl trimethoxy silicane
The boronic acid compounds of＜use 〉
C: ortho-boric acid
Claims (11)
1. polyacetal resin composite, it is characterized in that, in polyacetal resin composition (A) 100 weight parts, cooperating in the polyacetal resin composite of category of glass inorganic filling material (B) 3～200 weight parts, further cooperate boronic acid compounds (C) 0.001～1.0 weight part, simultaneously, this polyacetal resin composition (A) is that ratio with modified polyacetal resin (A2) 0.1～20 weight part that has the hydroxyl of 30～2000mmol/kg in polyacetal resin (A1) 99.9～80 weight parts of the hydroxyl that has 0～20mmol/kg in the molecule and the molecule constitutes.
2. polyacetal resin composite as claimed in claim 1, wherein, polyacetal resin (A1) is by with three
Alkane and be selected from cyclic ether and multipolymer that the compound copolymerization in the cyclic formals obtains with hydroxyl.
3. polyacetal resin composite as claimed in claim 1 or 2, wherein, modified polyacetal resin (A2) is by in the presence of the compound with hydroxyl, with three
Alkane be selected from the multipolymer that cyclic ether with hydroxyl and the compound copolymerization in the cyclic formals obtain.
4. polyacetal resin composite as claimed in claim 1 or 2, wherein, modified polyacetal resin (A2) is by with three
Alkane, be selected from the multipolymer that cyclic ether and the compound in the cyclic formals with hydroxyl and the cyclic formals copolymerization that contains hydroxyl obtain.
5. polyacetal resin composite as claimed in claim 4, wherein, the cyclic formals that contains hydroxyl is a Sericosol N.
6. polyacetal resin composite as claimed in claim 1 or 2, wherein, modified polyacetal resin (A2) is the multipolymer that obtains by following: with three
Alkane, be selected from the compound copolymerization that cyclic ether and the compound in the cyclic formals with hydroxyl and the hydroxyl of the cyclic formals that contains hydroxyl are formed by acidylate or silanization; prepare the multipolymer that side chain has acyl group or silyl thus; then; when side chain has acyl group with basic cpd, when side chain has silyl, this multipolymer is handled with acidic cpd; part or all that makes acyl group or silyl thus is decomposed to form hydroxyl, thus the described multipolymer that obtains.
7. polyacetal resin composite as claimed in claim 6, wherein, the hydroxyl that contains the cyclic formals of hydroxyl is the Sericosol N acetic ester by the compound that acidylate or silanization form.
8. as any described polyacetal resin composite in the claim 1～7, wherein, category of glass inorganic filling material (B) is for being selected from least a in glass fibre, granulated glass sphere, milled glass fiber and the sheet glass.
9. as any described polyacetal resin composite in the claim 1～8, wherein, category of glass inorganic filling material (B) carried out surface treatment with being selected from least a in silane coupling agent and the titante coupling agent.
10. as any described polyacetal resin composite in the claim 1～9, wherein, boronic acid compounds (C) is to be selected from least a in ortho-boric acid, metaboric acid, tetraboric acid and the boron trioxide.
11. as any described polyacetal resin composite in the claim 1～10, wherein, polyacetal resin composition (A) ratio with 0.01～3 weight part in its 100 weight part contains the polyacetal resin (A3) with branch or crosslinking structure.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/JP2008/068123 WO2010035351A1 (en) | 2008-09-29 | 2008-09-29 | Polyacetal resin composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102131865A true CN102131865A (en) | 2011-07-20 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008801308489A Pending CN102131865A (en) | 2008-09-29 | 2008-09-29 | Polyacetal resin composition |
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| Country | Link |
|---|---|
| CN (1) | CN102131865A (en) |
| WO (1) | WO2010035351A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108603007A (en) * | 2016-03-31 | 2018-09-28 | 宝理塑料株式会社 | Polyacetal resin composite |
| CN108699318A (en) * | 2016-03-31 | 2018-10-23 | 宝理塑料株式会社 | Polyacetal resin composite |
| CN112714774A (en) * | 2018-11-28 | 2021-04-27 | 宝理塑料株式会社 | Polyacetal resin composition and method for producing polyacetal resin composition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MX344215B (en) | 2010-10-14 | 2016-12-07 | Celanese Sales Germany Gmbh | Coupled glass-fiber reinforced polyoxymethylene. |
| CN102558755A (en) | 2010-10-14 | 2012-07-11 | 提克纳有限公司 | Glass-fiber reinforced polyoxymethylene |
| EP2581408B1 (en) | 2011-10-14 | 2015-07-29 | Ticona GmbH | Tribologically modified glass-fiber reinforced polyoxymethylene |
| EP2653497B1 (en) | 2012-04-17 | 2015-01-28 | Ticona GmbH | Weather resistant polyoxymethylene compositions |
| US9062183B2 (en) | 2012-12-20 | 2015-06-23 | Ticona Gmbh | Fiber reinforced polyoxymethylene composition with improved thermal properties |
| US10196577B2 (en) | 2015-09-30 | 2019-02-05 | Celanese Sales Germany Gmbh | Low friction squeak free assembly |
| CN110741045A (en) | 2017-06-16 | 2020-01-31 | 塞拉尼斯销售德国有限公司 | Reinforced polyoxymethylene compositions with low emissions |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5043398A (en) * | 1989-05-12 | 1991-08-27 | Hoechst Celanese Corporation | Grafting of functional compounds onto functional oxymethylene polymer backbones, with diisocyanate coupling agents, and the graft polymers thereof |
| US4975519A (en) * | 1989-05-12 | 1990-12-04 | Hoechst Celanese Corporation | Novel polyacetal terpolymers of trioxane and alpha, alpha- and alpha, beta-isomers of glycerol formal and functional derivatives thereof |
| JP3224156B2 (en) * | 1992-12-28 | 2001-10-29 | ポリプラスチックス株式会社 | Polyacetal resin composition |
| JP3086360B2 (en) * | 1993-06-08 | 2000-09-11 | ポリプラスチックス株式会社 | Modified polyacetal copolymer, method for producing the same, and composition containing the same |
| JP3285480B2 (en) * | 1995-09-29 | 2002-05-27 | ポリプラスチックス株式会社 | Polyacetal resin composition |
| JP3285481B2 (en) * | 1995-12-27 | 2002-05-27 | ポリプラスチックス株式会社 | Automotive components made of polyacetal resin |
| JP5005159B2 (en) * | 2003-06-04 | 2012-08-22 | ポリプラスチックス株式会社 | Polyacetal resin composition |
| JP2008044995A (en) * | 2006-08-11 | 2008-02-28 | Polyplastics Co | Polyacetal resin composition |
-
2008
- 2008-09-29 CN CN2008801308489A patent/CN102131865A/en active Pending
- 2008-09-29 WO PCT/JP2008/068123 patent/WO2010035351A1/en active Application Filing
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108603007A (en) * | 2016-03-31 | 2018-09-28 | 宝理塑料株式会社 | Polyacetal resin composite |
| CN108699318A (en) * | 2016-03-31 | 2018-10-23 | 宝理塑料株式会社 | Polyacetal resin composite |
| CN108699318B (en) * | 2016-03-31 | 2021-04-30 | 宝理塑料株式会社 | Polyacetal resin composition |
| US11142637B2 (en) | 2016-03-31 | 2021-10-12 | Polyplastics Co., Ltd. | Polyacetal resin composition |
| CN112714774A (en) * | 2018-11-28 | 2021-04-27 | 宝理塑料株式会社 | Polyacetal resin composition and method for producing polyacetal resin composition |
| CN112714774B (en) * | 2018-11-28 | 2023-08-25 | 宝理塑料株式会社 | Polyacetal resin composition and method for producing polyacetal resin composition |
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| WO2010035351A1 (en) | 2010-04-01 |
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