CN105237943A - Rigidity-reinforced polyformaldehyde composite material and preparation method thereof - Google Patents
Rigidity-reinforced polyformaldehyde composite material and preparation method thereof Download PDFInfo
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- CN105237943A CN105237943A CN201510655158.7A CN201510655158A CN105237943A CN 105237943 A CN105237943 A CN 105237943A CN 201510655158 A CN201510655158 A CN 201510655158A CN 105237943 A CN105237943 A CN 105237943A
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Abstract
The invention discloses a rigidity-reinforced polyformaldehyde composite material including 70-95 parts by weight of polyformaldehyde, 5-30 parts by weight of a toughening elastomer and 0.2-1.0 part by weight of a modification compatilizer. The invention also provides a preparation method of the rigidity-reinforced polyformaldehyde composite material. Through adding the special modification compatilizer, a compatibility effect of basis resin and the rigidity reinforcing modifier in the composite material is increased.
Description
Technical field
The invention belongs to polymer modification field, particularly relate to a kind of rigidity reinforced polyformaldehyde composite material and preparation method thereof.
Background technology
Polyformaldehyde resin molecular structure is regular, degree of crystallinity is high, thus has high tensile, high modulus in flexure, high rigidity, excellent combination property, is widely used in automobile, electric, office equipment, mechanical engineering and household appliances field.Polyformaldehyde resin has very consequence in preparation various rotational components etc.
Although other resins or material relatively, as polyethylene, polypropylene, Acrylnitrile-Butadiene-Styrene, polystyrene, polyvinyl chloride, polyformaldehyde resin has higher rigidity or modulus, but preparing high abrasion or high strength goods, during as extraordinary gear, bearing, mechanical linkage parts, electrical component, still need the rigidity or the modulus that improve polyformaldehyde resin.
In order to improve rigidity or the modulus of general polyformaldehyde resin, can utilize the rigidity enhanced, modified method that macromolecular material is conventional, major measure has: 1. utilize chemical reaction, on the main chain that the macromole material with specific functional groups being grafted on macromolecular material connects; 2. utilize blended remodeling, will the material of high-modulus be had, according to predetermined ratio, by different blend methods, make blend.Because polyoxymethylene molecular chain is straight chain, molecular chain lacks the functional group that can react, therefore in raising polyoxymethylene rigidity, adopt chemical process copolymerization Third monomer or utilize graft reaction all to rarely have achievement, the method of extensive employing utilizes melt blending to prepare blend alloy, mixed under shearing force field effect by the polymkeric substance that can improve polyoxymethylene base resin with other or improve polyoxymethylene base resin rigidity or modulus, the homogenize material of high rigidity or high-modulus is dispersed in polyformaldehyde resin, thus obtains rigidity reinforced polyformaldehyde composite material.When material is subject to stress, polyoxymethylene meets high rigidity in material or high modulus material can play skeleton function, thus increases substantially the stretch-proof of matrix material, counter-bending or wear resisting property.
For preparing rigidity reinforced polyformaldehyde composite material, some polyoxymethylene manufacturing enterprises and research institution have carried out corresponding work equally.CN101343396B discloses a kind of method of fiberglass reinforced polyoxymethylene, adopt alkali-free glass fiber, medium-alkali glass fiber or chemical modification glass as rigidity enhanced, modified dose in the method, utilizing silane coupling agent to increase consistency, improving the stripping result of the course of processing by adding film former.CN1056698A disclose improve glass and polyoxymethylene with nylon resin prepare to the same sex method strengthening polyoxymethylene.CN102108182A discloses a kind of drive and transmission parts polyformaldehyde material, this patent improves the rigidity of material by adding glass fibre and potassium titanate crystal whisker in polyformaldehyde resin, improve toughness with polyoxyethylene and ultrahigh molecular weight polyethylene(UHMWPE), glass improves the consistency with polyformaldehyde resin by coupling agent treatment.CN101759957B discloses a kind of preparation method strengthening wear-resistant polyformaldehyde composition, improve the rigidity of polyoxymethylene with glass fibre in the method, improving the wear resisting property of material by adding tetrafluoroethylene, with the addition of urethane to improve the toughness of material.But, in the prior art, although introduce rigidity enhanced, modified dose to improve the rigidity of polyoxymethylene, the problem of consistency both prior art does not solve at present well.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of rigidity reinforced polyformaldehyde composite material and preparation method thereof, to prepare high performance rigidity reinforced polyformaldehyde composite material.
An aspect for achieving the above object, adopts following technical scheme:
A kind of rigidity reinforced polyformaldehyde composite material, comprises the component of following weight part:
Polyoxymethylene 70 ~ 95
Rigidity enhanced, modified dose 5 ~ 30
Modification compatilizer 0.2 ~ 1.0
Wherein, described modification compatilizer is calcium maleate graft copolymer and/or polyol.
According to polyformaldehyde composite material of the present invention, preferably, described matrix material also comprises the one package stabilizer of 0.4 ~ 1.2 weight part, and described one package stabilizer comprises the component of following weight percent:
According to polyformaldehyde composite material of the present invention, preferably, described one package stabilizer is made up of the material of the component of following weight percent:
According to polyformaldehyde composite material of the present invention, preferably, described matrix material comprises the component of following weight part:
According to polyformaldehyde composite material of the present invention, preferably, described maleic anhydride graft copolymer is selected from maleic anhydride grafted polystyrene, maleic anhydride stem grafting polyolefin, maleic anhydride connect in poly-branch vinyl acetate, maleic anhydride inoculated polypropylene acid amides and maleic anhydride graft styrene butadiene-vinyl cyanide one or more; Described polyol be selected from TriMethylolPropane(TMP), tetramethylolmethane base triol and dimethoxy benzidine polymeric derivative one or more.
According to polyformaldehyde composite material of the present invention, preferably, described compatible modifier is calcium maleate graft copolymer.
According to polyformaldehyde composite material of the present invention, preferably, the firm chemicals of described increasing are selected from one or more in glass fibre, potassium titanate crystal whisker, calcium sulfate crystal whiskers, carbon fiber and carbon nanotube.
According to polyformaldehyde composite material of the present invention, preferably, described formaldehyde absorbent be selected from trimeric cyanamide, trimeric cyanamide formal, diethyl triamine, Dyhard RU 100, the halo derivatives of trimeric cyanamide or the alcohol of trimeric cyanamide in derivative one or more;
Described fomic acid absorber be selected from zinc oxide, aluminum oxide, Sodium Benzoate, calcium stearate, Zinic stearas and Magnesium Stearate one or more;
Described anti-floating fiber lubricant be selected from dimethyl silicone oil, phenyl silicone oil, methoxyl group silicone oil, ethylene bis stearamide, ethylene two amine hydroxybenzene, ethylene bis stearamide graft copolymer, silicone powder and polyethylene wax one or more;
Described oxidation inhibitor is selected from four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid octadecyl ester, N, N '-hexa-methylene two (3, 5-di-t-butyl-4-hydroxybenzene propionic acid amide), tetramethylolmethane four (3-lauryl thiopropionate), triglycol two [3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester], 2-methylene-bis (4-methyl-6-tert-butylphenol), two [the 3-(3 of hexylene glycol, 5-di-tert-butyl-hydroxy phenyl) propionic ester] and 1, 3, 5-trimethylammonium-2, 4, 6-tri-(3, 5-di-tert-butyl-4-hydroxyl benzyl) one or more in benzene.
Present invention also offers a kind of preparation method of above-mentioned rigidity reinforced polyformaldehyde composite material, comprise the steps:
(1) component of one package stabilizer is pressed the blended granulation of proportioning, obtain one package stabilizer;
(2) by proportioning, the one package stabilizer that polyoxymethylene, modification compatilizer and step (1) obtain is mixed in mixing machine, the mixture obtained and rigidity enhanced, modified dose are sent into twin screw extruder respectively by feeder, through fusion plastification, extrude pelletizing, thus obtain polyformaldehyde composite material.
Preparation in accordance with the present invention, preferably, double-screw extruder screw rotating speed is 100 ~ 1000r/min, and extruder temperature is 160 ~ 200 DEG C, and cooling temperature is 20 DEG C ~ 80 DEG C.
The present invention adopts the method for mechanical blending to mix rigidity enhanced, modified dose with polyoxymethylene base resin, is improved the com-patibilising effect of each component of matrix material by the modification compatilizer mixed with polyoxymethylene in advance further.
In the present invention, special maleic anhydride graft copolymer or the polyol of adopting is as modification compatilizer, to improve com-patibilising effect; The present invention is Promethean on the other hand have employed the one package stabilizer having and inhale aldehyde, inhale acid and lubricating function; In addition the preparation of rigidity reinforced polyformaldehyde composite material of the present invention adopts general twin screw extruder, need not add the equipment of other complexity, be convenient to enforcement of the present invention and popularization.
Embodiment
Rigidity reinforced polyformaldehyde composite material of the present invention, by adding rigidity enhanced, modified dose in polyoxymethylene, thus improve its rigidity, simultaneously, consistency property between rigidity enhanced, modified dose and polyoxymethylene is improved, to regulate the character such as the rigidity of polyoxymethylene further by adding special modification compatilizer.
Rigidity reinforced polyformaldehyde composite material of the present invention, comprises the polyoxymethylene of 70 ~ 95 weight parts, preferably 75 ~ 90 weight parts, more preferably 78 ~ 84 weight parts; Rigidity reinforced polyformaldehyde composite material of the present invention also comprises rigidity enhanced, modified dose of 5 ~ 30 weight parts, preferably 10 ~ 25 weight parts, more preferably 14 ~ 20 weight parts, and described rigidity enhanced, modified dose can be glass fibre, potassium titanate crystal whisker, calcium sulfate crystal whiskers, carbon fiber and carbon nanotube etc.
In rigidity reinforced polyformaldehyde composite material of the present invention, also comprise the modification compatilizer of 0.2 ~ 1.0 weight part, preferably 0.4 ~ 0.8 weight part, more preferably 0.5 ~ 0.6 weight part, described modification compatilizer is calcium maleate graft copolymer and/or polyol.Preferably, described maleic anhydride graft copolymer is selected from one or more in maleic anhydride grafted polystyrene, maleic anhydride stem grafting polyolefin, maleic anhydride grafted ethene-vinyl acetate, maleic anhydride inoculated polypropylene acid amides and maleic anhydride graft styrene butadiene-vinyl cyanide, described polyol is selected from TriMethylolPropane(TMP), one or more in tetramethylolmethane base triol and dimethoxy benzidine polymeric derivative, these modification compatilizers are different from the modification compatilizer that silane coupling agent etc. is usually used in improving consistency between rigidity enhanced, modified dose and polyoxymethylene, although silane coupling agent is easy and the radical reaction on glass surface, but it is poor with polyoxymethylene consistency, easily move out from polyoxymethylene surface, and the maleic anhydride graft copolymer that the present invention selects or polyol not only have good reactivity with glass surface group, and it is better with polyformaldehyde resin consistency, not easily move outside from polyoxymethylene.Further preferably, described modification compatilizer is calcium maleate graft copolymer.
In rigidity reinforced polyformaldehyde composite material of the present invention, preferably also comprise the one package stabilizer of 0.4 ~ 1.2 weight part, preferably 0.5 ~ 1.0 weight part, more preferably 0.6 ~ 0.8 weight part, in the present invention, described one package stabilizer comprises formaldehyde absorbent, fomic acid absorber, anti-floating fiber lubricant and oxidation inhibitor.
Wherein, the content of described formaldehyde absorbent is 20 ~ 40wt% of described one package stabilizer, is preferably 25 ~ 35wt%, is more preferably 26 ~ 33wt%.Described formaldehyde absorbent can be the conventional formaldehyde absorbent in this area, be preferably selected from trimeric cyanamide, trimeric cyanamide formal, diethyl triamine, Dyhard RU 100, the halo derivatives of trimeric cyanamide or the alcohol of trimeric cyanamide in derivative one or more.
The content of described fomic acid absorber is 4 ~ 10wt% of described one package stabilizer, is preferably 6 ~ 8wt%, is more preferably 6.3 ~ 7.5wt%.Described fomic acid absorber can be the conventional fomic acid absorber in this area, is preferably selected from one or more in zinc oxide, aluminum oxide, Sodium Benzoate, calcium stearate, Zinic stearas and Magnesium Stearate.
The content of described anti-floating fiber lubricant is 8 ~ 16wt% of described one package stabilizer, is preferably 9 ~ 14wt%, is more preferably 10 ~ 12wt%.Described lubricant releasing agent can be the conventional lubricant releasing agent in this area, is preferably selected from one or more in dimethyl silicone oil, phenyl silicone oil, methoxyl group silicone oil, ethylene bis stearamide, ethylene two amine hydroxybenzene, ethylene bis stearamide graft copolymer, silicone powder and polyethylene wax.
The content of described oxidation inhibitor is 40 ~ 60wt% of described one package stabilizer, is preferably 44 ~ 57wt%, is more preferably 47 ~ 51wt%.The oxidation inhibitor that described oxidation inhibitor can be commonly used for this area, be preferably selected from four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid octadecyl ester, N, N '-hexa-methylene two (3, 5-di-t-butyl-4-hydroxybenzene propionic acid amide), tetramethylolmethane four (3-lauryl thiopropionate), triglycol two [3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester], 2-methylene-bis (4-methyl-6-tert-butylphenol), two [the 3-(3 of hexylene glycol, 5-di-tert-butyl-hydroxy phenyl) propionic ester] and 1, 3, 5-trimethylammonium-2, 4, 6-tri-(3, 5-di-tert-butyl-4-hydroxyl benzyl) one or more in benzene.
The advantage of this one package stabilizer is adopted to have the following aspects: (1) is by the formaldehyde absorption effect of one package stabilizer, reduce generation and the release of formaldehyde gas in matrix material production and Downstream processing, this contributes to keeping composite property, reduces the injury to human body in matrix material production, Downstream processing and user's use procedure; (2) by the formaldehyde absorption effect of one package stabilizer, contribute to the generation reducing free formic acid in matrix material production, Downstream processing and user's use procedure, thus avoid the chain type caused by carboxyl free radical occurred owing to there is free formic acid in matrix material to degrade; (3) by the fine lubricating function of the anti-floating of one package stabilizer, improve the glass problem of leakage of matrix material, the smooth performance of product surface, contribute to the production efficiency improving Downstream processing enterprise; (4) antioxygenation of one package stabilizer can improve matrix material at the thermo-oxidative stability produced and in Downstream processing.
It will be understood by those skilled in the art that described one package stabilizer can also comprise other additives, as pearl filler, tinting material, UV absorption agent etc., to improve composite property further.
In the preparation process of rigidity reinforced polyformaldehyde composite material of the present invention, need to add different types of interpolation, due to the form of various additive, density and character difference all to some extent, thus how being added to uniformly in polyoxymethylene by additive is very important problem.The present invention first by the blended granulation in advance of the required various additives added, obtains one package stabilizer, and then joins in polyoxymethylene.In a preferred embodiment, formaldehyde absorbent, fomic acid absorber, profit anti-floating fiber lubricant and oxidation inhibitor sent in proportion stirring in mixing machine, mix, the mixing speed of described mixing machine is 500 ~ 1500r/min, then extruder grain in pair roller type screw extruder, obtains one package stabilizer agent particle.
When preparing rigidity reinforced polyformaldehyde composite material of the present invention, by proportioning by polyoxymethylene, the pre-mixing in mixing machine of modification compatilizer, the mixture obtained and rigidity enhanced, modified dose are sent into twin screw extruder respectively by feeder, through fusion plastification, extrude pelletizing, thus obtain rigidity reinforced polyformaldehyde composite material.Wherein, when needs add one package stabilizer, by described one package stabilizer and polyoxymethylene, the pre-mixing in mixing machine of modification compatilizer, mixture is obtained.
Preferably, double-screw extruder screw rotating speed is 100 ~ 1000r/min, and extruder temperature is 160 ~ 200 DEG C, and cooling temperature is 20 DEG C ~ 80 DEG C.
By following examples, more detailed description is made to the present invention now, but the present invention is not limited to these embodiments.
Raw materials usedly in following examples to be described as follows:
Polyoxymethylene: model MC90, coal chemical industry branch office of Ningxia Coal Industry Group company limited of Shenhua;
Glass fibre: model 500, Jushi Group Co., Ltd.;
Potassium titanate crystal whisker: model UM-T-50, Shanghai associating Materials Co., Ltd;
Calcium sulfate crystal whiskers: model NP-M01, Shanghai Feng Zhu trade Co., Ltd;
Maleic anhydride graft polyvinyl acetate (PVA): model ST-3, Nanjing Su Tai polymer scientific & technical corporation;
Maleic anhydride grafted polystyrene: model KT-5, Sheyang Ketong Plastic Co., Ltd.;
Maleic anhydride graft styrene butadiene-vinyl cyanide: model KT-2, Sheyang Ketong Plastic Co., Ltd.;
TriMethylolPropane(TMP): sea specialization factory of Jihua Group Co, purity >=98%;
Dimethoxy benzidine polymkeric substance: Yan Tuo bio tech ltd, Shanghai, purity >=98%, hydroxyl value 1240-1260mgKOH/g;
Vinyltrimethoxy silane: trade mark A-171, Nanjing Luo En silicon materials company limited, purity >=98%, molecular-weight average 313.3;
γ-aminopropyl triethoxysilane: model A110, Qufu morning twilight Chemical Co., Ltd., purity >=98%;
In following examples, without special instruction, agents useful for same is analytical pure.
The performance test of reinforced polyformaldehyde matrix material:
According to table 1 testing method, analytical test is carried out to the mechanical property of reinforced polyformaldehyde matrix material
The testing method of table 1 polyoxymethylene
Embodiment 1
The preparation of one package stabilizer:
1. by 338g formaldehyde absorbent trimeric cyanamide, 61g fomic acid absorber zinc oxide, 452g oxidation inhibitor triglycol two [3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester], 108g anti-floating fiber lubricant dimethyl silicone oil adds homogenizer (the Europe Bei Te plastics machinery company limited of 3L, model SHR-10A, lower same) in, under rotating speed is 1200 revs/min, mix;
2. the one package stabilizer mixed is joined extrusion shaping machine (Xin You mechanical means Manufacturing Co., Ltd of Jiangyin City, model S-40, lower with) in, extrude, pelletizing obtain one package stabilizer particle.
The preparation of rigidity reinforced polyformaldehyde composite material:
By 3.12kg polyoxymethylene, 12g maleic anhydride grafted polystyrene, 16g one package stabilizer joins in high-speed mixer and mixes, and mixing machine stir speed (S.S.) is 1500r/min; Then the component after mixing is joined in the main feeder of twin screw extruder, 350g glass fibre adds from auxiliary feeder, above-mentioned material is through extruding pelletization, obtain rigidity reinforced polyformaldehyde composite material, twin screw extruder (Ke Beilong (Shanghai) Co., Ltd., model ZSK26K10.6, down together) screw speed is 650r/min, extruder screw each section of temperature is 165 DEG C, 170 DEG C, 175 DEG C, 180 DEG C, 185 DEG C, 180 DEG C, 175 DEG C, and cooling temperature is 40 DEG C.
The performance test results of gained matrix material is see table 2.
Embodiment 2
The preparation of one package stabilizer:
1. by 276g formaldehyde absorbent trimeric cyanamide, 54g fomic acid absorber Zinic stearas, 248g oxidation inhibitor four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 132g oxidation inhibitor tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester, the two amine hydroxybenzene of 130g anti-floating fiber lubricant ethylene adds in the homogenizer of 3L, under rotating speed is 900 revs/min, mix;
2. the one package stabilizer mixed is joined in extrusion shaping machine, extrude, pelletizing obtains one package stabilizer particle.
The preparation of rigidity reinforced polyformaldehyde composite material:
By 2.98kg polyoxymethylene, 21g maleic anhydride grafted polystyrene, 28g one package stabilizer joins in high-speed mixer and mixes, and mixing machine stir speed (S.S.) is 1600r/min; Then the component after mixing is joined in the main feeder of twin screw extruder, 525g glass fibre adds from auxiliary feeder, above-mentioned material is through extruding pelletization, obtain rigidity reinforced polyformaldehyde composite material, double-screw extruder screw rotating speed is 630r/min, extruder screw each section of temperature is 165 DEG C, 170 DEG C, 175 DEG C, 180 DEG C, 185 DEG C, 180 DEG C, 175 DEG C, and cooling temperature is 40 DEG C.
The performance test results of gained matrix material is see table 2.
Embodiment 3
The preparation of one package stabilizer:
1. by 285g formaldehyde absorbent diethyl triamine, 76g fomic acid absorber calcium stearate, 245g oxidation inhibitor triglycol two [3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester], 234g oxidation inhibitor four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, the two amine hydroxybenzene graft copolymer of 105g anti-floating fiber lubricant ethylene adds in the homogenizer of 3L, under rotating speed is 1000 revs/min, mixes;
2. the one package stabilizer mixed is joined in extrusion shaping machine, extrude, pelletizing obtains one package stabilizer particle.
The preparation of rigidity reinforced polyformaldehyde composite material:
By 2.75kg polyoxymethylene, 21g maleic anhydride grafted ethene-vinyl acetate, 28g one package stabilizer joins in high-speed mixer and mixes, and mixing machine stir speed (S.S.) is 1600r/min; Then the component after mixing is joined in the main feeder of twin screw extruder, 700g glass fibre adds from auxiliary feeder, above-mentioned material is through extruding pelletization, obtain rigidity reinforced polyformaldehyde composite material, double-screw extruder screw rotating speed is 630r/min, extruder screw each section of temperature is 168 DEG C, 172 DEG C, 175 DEG C, 180 DEG C, 185 DEG C, 180 DEG C, 175 DEG C, and cooling temperature is 45 DEG C.
The performance test results of gained matrix material is see table 2.
Embodiment 4
The preparation of one package stabilizer:
1. by 235g formaldehyde absorbent trimeric cyanamide, 67g fomic acid absorber zinc oxide, 214g oxidation inhibitor triglycol two [3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester], 168g oxidation inhibitor four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 132g oxidation inhibitor tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester, 85g anti-floating fiber lubricant polyethylene wax adds in the homogenizer of 3L, under rotating speed is 1250 revs/min, mix;
2. the one package stabilizer mixed is joined in extrusion shaping machine, extrude, pelletizing obtains one package stabilizer particle.
The preparation of rigidity reinforced polyformaldehyde composite material:
By 2.58kg polyoxymethylene, 17.5g maleic anhydride graft styrene butadiene-vinyl cyanide, 28g one package stabilizer joins in high-speed mixer and mixes, and mixing machine stir speed (S.S.) is 1600r/min; Then the component after mixing is joined in the main feeder of twin screw extruder, 875g glass fibre adds from auxiliary feeder, above-mentioned material is through extruding pelletization, obtain rigidity reinforced polyformaldehyde composite material, double-screw extruder screw rotating speed is 650r/min, extruder screw each section of temperature is 168 DEG C, 172 DEG C, 175 DEG C, 180 DEG C, 185 DEG C, 180 DEG C, 175 DEG C, and cooling temperature is 45 DEG C.
The performance test results of gained matrix material is see table 2.
Embodiment 5
The preparation of one package stabilizer:
1. by 342g formaldehyde absorbent trimeric cyanamide, 57g fomic acid absorber zinc oxide, 437g oxidation inhibitor triglycol two [3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester], the two amine hydroxybenzene graft copolymer of 114g anti-floating fiber lubricant ethylene adds in the homogenizer of 3L, under rotating speed is 1200 revs/min, mix;
2. the one package stabilizer mixed is joined in extrusion shaping machine, extrude, pelletizing obtains one package stabilizer particle.
The preparation of rigidity reinforced polyformaldehyde composite material:
By 3.12kg polyoxymethylene, 14g TriMethylolPropane(TMP), 21g one package stabilizer joins in high-speed mixer and mixes, and mixing machine stir speed (S.S.) is 1500r/min; Then the component after mixing is joined in the main feeder of twin screw extruder, 350g potassium titanate crystal whisker adds from auxiliary feeder, above-mentioned material is through extruding pelletization, obtain rigidity reinforced polyformaldehyde composite material, double-screw extruder screw rotating speed is 650r/min, extruder screw each section of temperature is 168 DEG C, 172 DEG C, 175 DEG C, 180 DEG C, 185 DEG C, 180 DEG C, 175 DEG C, and cooling temperature is 40 DEG C.
The performance test results of gained matrix material is see table 2.
Embodiment 6
The preparation of one package stabilizer:
1. by 342g formaldehyde absorbent trimeric cyanamide, 57g fomic acid absorber zinc oxide, 437g oxidation inhibitor triglycol two [3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester], 114g anti-floating fiber lubricant silicone powder adds in the homogenizer of 3L, under rotating speed is 1200 revs/min, mix;
2. the one package stabilizer mixed is joined in extrusion shaping machine, extrude, pelletizing obtains one package stabilizer particle.
The preparation of rigidity reinforced polyformaldehyde composite material:
By 3.12kg polyoxymethylene, 12g dimethoxy benzidine polymkeric substance, 21g one package stabilizer joins in high-speed mixer and mixes, and mixing machine stir speed (S.S.) is 1500r/min; Then the component after mixing is joined in the main feeder of twin screw extruder, 350g calcium sulfate crystal whiskers adds from auxiliary feeder, above-mentioned material is through extruding pelletization, obtain rigidity reinforced polyformaldehyde composite material, double-screw extruder screw rotating speed is 650r/min, extruder screw each section of temperature is 168 DEG C, 172 DEG C, 175 DEG C, 180 DEG C, 185 DEG C, 180 DEG C, 175 DEG C, and cooling temperature is 40 DEG C.
The performance test results of gained matrix material is see table 2.
Comparative example 1
By 3.12kg polyoxymethylene, 16g oxidation inhibitor triglycol two [3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester] joins in high-speed mixer and mixes, and mixing machine stir speed (S.S.) is 1500r/min; Then the component after mixing is joined in the main feeder of twin screw extruder, 350g glass fibre adds from auxiliary feeder, above-mentioned material is through extruding pelletization, obtain rigidity reinforced polyformaldehyde composite material, double-screw extruder screw rotating speed is 650r/min, extruder screw each section of temperature is 168 DEG C, 172 DEG C, 175 DEG C, 180 DEG C, 185 DEG C, 180 DEG C, 175 DEG C, and cooling temperature is 40 DEG C.
The performance test results of gained matrix material is see table 2.
Comparative example 2
By 3.12kg polyoxymethylene, 16g oxidation inhibitor triglycol two [3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester] joins in high-speed mixer and mixes, and mixing machine stir speed (S.S.) is 1500r/min; Then the component after mixing is joined in the main feeder of twin screw extruder, 350g potassium titanate crystal whisker adds from auxiliary feeder, above-mentioned material is through extruding pelletization, obtain rigidity reinforced polyformaldehyde composite material, double-screw extruder screw rotating speed is 650r/min, extruder screw each section of temperature is 168 DEG C, 172 DEG C, 175 DEG C, 180 DEG C, 185 DEG C, 180 DEG C, 175 DEG C, and cooling temperature is 40 DEG C.
The performance test results of gained matrix material is see table 2.
Comparative example 3
Be with the difference of embodiment 1, modification compatilizer used is vinyltrimethoxy silane.
The performance test results of gained matrix material is see table 2.
Comparative example 4
Be with the difference of embodiment 5, modification compatilizer used is γ-aminopropyl triethoxysilane.
The performance test results of gained matrix material is see table 2.
Table 2 implementation column and comparative example test result
Claims (10)
1. a rigidity reinforced polyformaldehyde composite material, comprises the component of following weight part:
Polyoxymethylene 70 ~ 95
Rigidity enhanced, modified dose 5 ~ 30
Modification compatilizer 0.2 ~ 1.0
Wherein, described modification compatilizer is calcium maleate graft copolymer and/or polyol.
2. polyformaldehyde composite material according to claim 1, is characterized in that, described matrix material also comprises the one package stabilizer of 0.4 ~ 1.2 weight part, and described one package stabilizer comprises the component of following weight percent:
3. polyformaldehyde composite material according to claim 1, is characterized in that, described one package stabilizer is made up of the material of the component of following weight percent:
4. polyformaldehyde composite material according to claim 1, is characterized in that, described matrix material comprises the component of following weight part:
5. polyformaldehyde composite material according to claim 1, it is characterized in that, described maleic anhydride graft copolymer is selected from maleic anhydride grafted polystyrene, maleic anhydride stem grafting polyolefin, maleic anhydride connect in poly-branch vinyl acetate, maleic anhydride inoculated polypropylene acid amides and maleic anhydride graft styrene butadiene-vinyl cyanide one or more; Described polyol be selected from TriMethylolPropane(TMP), tetramethylolmethane base triol and dimethoxy benzidine polymeric derivative one or more.
6. polyformaldehyde composite material according to claim 1, is characterized in that, described compatible modifier is calcium maleate graft copolymer.
7. polyformaldehyde composite material according to claim 1, is characterized in that, the firm chemicals of described increasing be selected from glass fibre, potassium titanate crystal whisker, calcium sulfate crystal whiskers, carbon fiber and carbon nanotube one or more.
8. polyformaldehyde composite material according to claim 1, is characterized in that,
Described formaldehyde absorbent be selected from trimeric cyanamide, trimeric cyanamide formal, diethyl triamine, Dyhard RU 100, the halo derivatives of trimeric cyanamide or the alcohol of trimeric cyanamide in derivative one or more;
Described fomic acid absorber be selected from zinc oxide, aluminum oxide, Sodium Benzoate, calcium stearate, Zinic stearas and Magnesium Stearate one or more;
Described anti-floating fiber lubricant be selected from dimethyl silicone oil, phenyl silicone oil, methoxyl group silicone oil, ethylene bis stearamide, ethylene two amine hydroxybenzene, ethylene bis stearamide graft copolymer, silicone powder and polyethylene wax one or more;
Described oxidation inhibitor is selected from four [β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, β-(3, 5-di-tert-butyl-hydroxy phenyl) propionic acid octadecyl ester, N, N '-hexa-methylene two (3, 5-di-t-butyl-4-hydroxybenzene propionic acid amide), tetramethylolmethane four (3-lauryl thiopropionate), triglycol two [3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) propionic ester], 2-methylene-bis (4-methyl-6-tert-butylphenol), two [the 3-(3 of hexylene glycol, 5-di-tert-butyl-hydroxy phenyl) propionic ester] and 1, 3, 5-trimethylammonium-2, 4, 6-tri-(3, 5-di-tert-butyl-4-hydroxyl benzyl) one or more in benzene.
9. the preparation method of the polyformaldehyde composite material according to any one of claim 1 ~ 8, comprises the steps:
(1) component of one package stabilizer is pressed the blended granulation of proportioning, obtain one package stabilizer;
(2) by proportioning, the one package stabilizer that polyoxymethylene, modification compatilizer and step (1) obtain is mixed in mixing machine, the mixture obtained and rigidity enhanced, modified dose are sent into twin screw extruder respectively by feeder, through fusion plastification, extrude pelletizing, thus obtain polyformaldehyde composite material.
10. preparation method according to claim 9, is characterized in that, double-screw extruder screw rotating speed is 100 ~ 1000r/min, and extruder temperature is 160 ~ 200 DEG C, and cooling temperature is 20 DEG C ~ 80 DEG C.
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