CN104341712A - Halogen-free low-warpage heat-resisting polyformaldehyde composite material and preparation method thereof - Google Patents
Halogen-free low-warpage heat-resisting polyformaldehyde composite material and preparation method thereof Download PDFInfo
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- CN104341712A CN104341712A CN201410581526.3A CN201410581526A CN104341712A CN 104341712 A CN104341712 A CN 104341712A CN 201410581526 A CN201410581526 A CN 201410581526A CN 104341712 A CN104341712 A CN 104341712A
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Abstract
The invention relates to a halogen-free low-warpage heat-resisting polyformaldehyde composite material, which is prepared from the following raw materials in parts by weight: 60-80 parts of polyformaldehyde, 10-25 parts of wollastonite, 10-20 parts of a chopped glass fiber, 2-10 parts of talcum powder masterbatch, 0.2-2 parts of a formaldehyde absorbent, 0.2-2 parts of an antioxidant, 0.4-2 parts of a complex lubricating agent, 0.2-1.5 parts of an ultra-dispersed coating agent and 0.4-5 parts of other adjuvants. The material prepared by the method disclosed by the invention is even in shrinkage, and high in dimensional accuracy; and the prepared product is smooth in surface and high in smoothness.
Description
Technical field
The invention belongs to technical field of plastic, be specifically related to high temperature resistant polyformaldehyde composite material of a kind of Halogen low warpage type and preparation method thereof.
Background technology
Polyoxymethylene (POM) does not a kind ofly have the high-density of side chain, the linear thermoplastic polymer of high crystalline, there is unique mechanical property and good self lubricity, little and the abrasion performance of coefficient of friction, have excellent water-resistance low with water-intake rate, good corrosion-resistant and self-lubricating and creep-resistant property, particularly there is outstanding fatigue performance, dimensional stability and excellent electrical property and low temperature resistant feature, can the performance such as (-40 ~ 100 DEG C) keep it to have in wide temperature range mechanics, chemistry and electricity.
Polyoxymethylene (POM) is as a kind of new type chemical material, and annual production is only second to nylon (PA) and polycarbonate (PC); It is alternative metals, the particularly desirable engineering plastics of the nonferrous metal and alloy goods such as copper, aluminium, zinc, be widely used in the traditional field such as machinofacture, electronic apparatus, precision instrument and daily necessities, at present just constantly to stride forward to the emerging field such as aerospace, automotive industry, but due to POM degree of crystallinity higher (generally reaching 70% ~ 85%), spherocrystal crystal grain is larger, notch sensitivity is large, notched Izod impact strength is lower, poor heat resistance, the performance deficiencies such as easy firing strongly limit the application of polyoxymethylene (POM).
Polyoxymethylene (POM) be uniquely do not rely in engineering plastics crude oil, with Coal Chemical Industry product methyl alcohol be raw material, with shorter technical process, the kind that can manufacture in a large number, it is extremely important C-1 chemistry derived product in Coal Chemical Industry product chain, development polyoxymethylene and downstream industry thereof meet the energy national conditions of the oil-poor rich coal weak breath of China, have important strategic importance.
Polyoxymethylene (POM) is although market demand is at home comparatively large, and be still in the starting stage to its research, development and production, output and performance far can not be met the need of market; And high-performance modified polyoxymethylene product, then basic dependence on import or controlled by the large multinational company of domestic individual proprietorship.Therefore polyoxymethylene modified research is carried out, the performance of further improvement polyoxymethylene product and quality, improve its added value and the market competitiveness, the individual demand of different user can be met, promote product high performance, become more meticulous, differential and systematize, not only very important to the expansion of polyoxymethylene (POM) application market, simultaneously very favourable to the technical progress of polyoxymethylene (POM) industry, also very crucial to the raising domestic polyoxymethylene manufacturing enterprise market competitiveness.
Summary of the invention
The object of the invention is to overcome existing technological deficiency and provide a kind of Halogen low warpage type high temperature resistant polyformaldehyde composite material, effectively solve the problems such as product buckling deformation that crystalline materials polyoxymethylene (POM) causes due to the larger internal stress self produced in moulding process, dimensional precision are not high, product surface unfairness, smooth finish is not high, use temperature conditional request is high.
In order to achieve the above object, the present invention adopts following technical scheme:
The invention provides the high temperature resistant polyformaldehyde composite material of a kind of Halogen low warpage type, be made up of the raw material of following weight part: polyoxymethylene 60 ~ 80, wollastonite 10 ~ 25, short glass fiber 10 ~ 20, talcum powder master batch 2 ~ 10, formaldehyde absorbent 0.2 ~ 2, oxidation inhibitor 0.2 ~ 2, composite lubricant 0.4 ~ 2, oversubscription are fallen apart coating 0.2 ~ 1.5, other auxiliary agents 0.4 ~ 5.
The high temperature resistant polyformaldehyde composite material of Halogen low warpage type, is made up of the raw material of following weight part: polyoxymethylene 65 ~ 75, wollastonite 10 ~ 20, short glass fiber 10 ~ 15, talcum powder master batch 2 ~ 6, formaldehyde absorbent 0.5 ~ 1, oxidation inhibitor 0.2 ~ 0.8, composite lubricant 0.4 ~ 1, oversubscription are fallen apart coating 0.2 ~ 0.8, other auxiliary agents 1 ~ 3.
Described polyoxymethylene is coal-based copolymerized methanal, and the mass flow rate of coal-based copolymerized methanal is 0.8 ~ 3g/min.
Described wollastonite is the fibrous wollastonite of particle diameter 10 ~ 30 μm, length-to-diameter ratio 10 ~ 20, pH value 7.2 ~ 7.8.
Described short glass fiber is the glass fibre of monfil diameter 8 ~ 12 μm, length 2 ~ 5mm.
Described talcum powder master batch is white no-load build, and talcum powder master batch is selected from the talcum powder master batch of particle diameter 2 ~ 5mm, length-to-diameter ratio 1 ~ 3, pH value 7.2 ~ 7.8.
Described composite lubricant is by three kinds or more in calcium stearate, stearic acid direactive glyceride, the two stearic acid amide (TAF) of ethylene and polyethylene wax, is wherein optimum with the two stearic acid amide (TAF) of calcium stearate, stearic acid direactive glyceride and ethylene according to 1:2:4.
Described oversubscription falls apart coating by organo-siloxane class coupling agent and titante coupling agent and aluminate coupling agent and white oil according to 3:(0.5 ~ 1): (0.5 ~ 1): (0 ~ 2) proportions.
Other auxiliary agents described are made up of the component of following weight part: silicone powder master batch 0.5 ~ 2 and Nucleating Agent 0.2 ~ 0.5.
Generally, Nucleating Agent can select the inorganic nucleators such as calcium carbonate, talcum powder, diatomite, also can select the organic nucleating agents such as carbon nanotube, polymeric amide, acefal homopolymer.
The preparation method of the high temperature resistant polyformaldehyde composite material of Halogen low warpage type, comprises the steps: (1) dried material: first by polyoxymethylene dehumidification system, raw material polyoxymethylene is carried out drying and processing, bake out temperature 60 ~ 100 DEG C, drying time 2 ~ 4h; Then the polyoxymethylene after oven dry is delivered to polyoxymethylene storage tank through blast system;
(2) mixture auxiliary agent: a. is 18 ~ 23 DEG C in temperature and takes the polyoxymethylene that processed through step (1) and the oversubscription coating that falls apart according to above-mentioned formula and put into mixing machine and stir, churning time 3 ~ 5min, stirring velocity 100 ~ 200r/min; B. be 18 ~ 23 DEG C in temperature according to above-mentioned formula, talcum powder master batch, oxidation inhibitor, composite lubricant, formaldehyde absorbent and other auxiliary addition agents to be put into mixing machine and be uniformly mixed, churning time 10 ~ 15min, stirring velocity 150 ~ 300r/min; Discharge after mixing and drop into addition agent storage tank;
(3) storehouse on auxiliary material: wollastonite is dropped into another addition agent storage tank according to above-mentioned formula, drops into position, side material storage tank according to above-mentioned formula by short glass fiber;
(4) extruding pelletization: each stock material enters high-speed mixer respectively through metering feeding and mixes except the feeding of side, then open side feeding storage tank low speed melt blending in twin screw side feeding machine metering feeding is in the screw combinations situation of twin screw extruder in moderate shear intensity is extruded, extrusion temperature 160 ~ 195 DEG C, screw speed 200 ~ 450r/min; Then water cooling bracing pelletizing, temperature of cooling water is 30 ~ 60 DEG C;
(5) dry packing: utilize temperature to be that the hot blast of 80 ~ 100 DEG C carries out backmixing drying, after after bolting the obtained high temperature resistant polyformaldehyde composite material of Halogen low warpage type be delivered to and wait storage tank of feeding; Finished goods warehouse is delivered to finally by metering packing.
Described short glass fiber carries out surface infiltration process by organo-siloxane class coupling agent and titante coupling agent and/mixed solvent that aluminate coupling agent configures according to a certain ratio, obtains that monfil diameter is 8 ~ 12 μm, length is the glass fibre of 2 ~ 5mm.
Described oxidation inhibitor is Hinered phenols antioxidant 245 or Hinered phenols antioxidant 1010.
Described formaldehyde absorbent is trimeric cyanamide.
compared with prior art, advantage of the present invention is:
(1) the high temperature resistant polyformaldehyde composite material of Halogen low warpage type of the present invention's acquisition, shrink evenly, dimensional precision is high, and product surface is smooth, highly polished; Molding shrinkage≤1.0, load heat-drawn wire (1.8MPa) >=150 DEG C, initial heat decomposition temperature >=410 DEG C, yielding stress >=80MPa, flexural strength >=110MPa, is suitable for manufacturing the Polyformaldehyde product of the different performance requirements such as low warpage, high temperature resistant, high strength.
(2) preparation method of the high temperature resistant polyformaldehyde composite material of Halogen of the present invention low warpage type makes the microtexture of material more stable, interface cohesion degree is higher, apparent property is superior, the anisotropy that lightening material orientation causes and the ununiform shrinkage caused because of crystallization, thus the warpage degree of reduction polyoxymethylene, moulding contraction degree of uniformity meet its service requirements.
(3) the present invention efficiently solves the product buckling deformation that crystalline materials polyoxymethylene (POM) causes due to the larger internal stress self produced in moulding process, improve the dimensional precision of polyoxymethylene product and shrink homogeneity, improve the thermostability of polyoxymethylene product and then meet polyoxymethylene product under higher temperature conditions, dimension precision requirement is high, surface finish smoothness requirements is high, the service requirements of part industry goods material Halogen, also will for widening the Application Areas of polyoxymethylene (POM) further, realize general-purpose plastics through engineering approaches, engineering plastics functionalization and the practical target of special engineering plastics play good pushing effect.
Embodiment
Below in conjunction with example, technical scheme of the present invention is further described, but described specific embodiment is only for explaining the present invention and in being used for limiting the scope of the invention.
The source of chemical reagent:
Polyoxymethylene Kaifeng Long Yu Chemical Co., Ltd. produces, MC90 type
The global wollastonite fibre Materials Co., Ltd in wollastonite Jiangxi produces
Short glass fiber Jushi Group Co., Ltd. produces, ECS11-4.5-500 type
Other chemical reagent is commercially available
embodiment 1
The high temperature resistant polyformaldehyde composite material of a kind of Halogen low warpage type, is made up of the raw material of following weight part: mass flow rate is the coal-based copolymerized methanal 65 of 0.95g/min; The fibrous wollastonite 15 of particle diameter 10 ~ 30 μm, length-to-diameter ratio 11, pH value 7.5; The short glass fiber 10 of monfil diameter 11 μm, length 4.5mm, talcum powder master batch 5, trimeric cyanamide 1, Hinered phenols antioxidant 1,010 0.5, composite lubricant 0.5, oversubscription are fallen apart coating 0.5, silicone 2 and polyoxymethylene 0.5; Wherein composite lubricant is with the two stearic acid amide of calcium stearate, stearic acid direactive glyceride and ethylene according to 1:2:4 proportions, and oversubscription falls apart coating by organo-siloxane class coupling agent and titante coupling agent and aluminate coupling agent and white oil according to 4:1:1:2 ratio mixed preparing.
embodiment 2
The high temperature resistant polyformaldehyde composite material of a kind of Halogen low warpage type, is made up of the raw material of following weight part: mass flow rate is the coal-based copolymerized methanal 70 of 0.95g/min; The fibrous wollastonite 10 of particle diameter 10 ~ 30 μm, length-to-diameter ratio 12, pH value 7.2; The short glass fiber 10 of monfil diameter 11 μm, length 4.5mm, talcum powder master batch 5, trimeric cyanamide 1, Hinered phenols antioxidant 1,010 0.5, composite lubricant 0.5, oversubscription are fallen apart coating 0.5, silicone 2 and polyoxymethylene 0.5; Wherein composite lubricant is with the two stearic acid amide of calcium stearate, stearic acid direactive glyceride and ethylene according to 1:2:4 proportions, and oversubscription falls apart coating by organo-siloxane class coupling agent and titante coupling agent and aluminate coupling agent and white oil according to 4:2:1:2 ratio mixed preparing.
embodiment 3
The high temperature resistant polyformaldehyde composite material of a kind of Halogen low warpage type, is made up of the raw material of following weight part: mass flow rate is the coal-based copolymerized methanal 65 of 0.95g/min; The fibrous wollastonite 20 of particle diameter 10 ~ 30 μm, length-to-diameter ratio 10, pH value 7.3; The short glass fiber 15 of monfil diameter 11 μm, length 4.5mm, talcum powder master batch 5, trimeric cyanamide 1, Hinered phenols antioxidant 1,010 0.5, composite lubricant 0.5, oversubscription are fallen apart coating 0.5, silicone 2 and polyoxymethylene 0.5; Wherein composite lubricant is with calcium stearate, stearic acid direactive glyceride and polyethylene wax according to 1:2:4 proportions, and oversubscription falls apart coating by organo-siloxane class coupling agent and titante coupling agent and aluminate coupling agent and white oil according to 4:1:1:2 ratio mixed preparing.
embodiment 4
The high temperature resistant polyformaldehyde composite material of a kind of Halogen low warpage type, is made up of the raw material of following weight part: mass flow rate is the coal-based copolymerized methanal 65 of 0.95g/min; The fibrous wollastonite 10 of particle diameter 10 ~ 30 μm, length-to-diameter ratio 12, pH value 7.4; The short glass fiber 15 of monfil diameter 11 μm, length 4.5mm, talcum powder master batch 5, trimeric cyanamide 1, Hinered phenols antioxidant 245 0.5, composite lubricant 0.5, oversubscription are fallen apart coating 0.5, silicone 2 and polyoxymethylene 0.5; Wherein composite lubricant is with calcium stearate, stearic acid direactive glyceride: the two stearic acid amide of ethylene: polyethylene wax is according to 1:2:4:3 proportions, and oversubscription falls apart coating by organo-siloxane class coupling agent and titante coupling agent and aluminate coupling agent and white oil according to 4:1:1:2 ratio mixed preparing.
embodiment 5
The high temperature resistant polyformaldehyde composite material of a kind of Halogen low warpage type, is made up of the raw material of following weight part: mass flow rate is the coal-based copolymerized methanal 70 of 0.95g/min; The fibrous wollastonite 15 of particle diameter 10 ~ 30 μm, length-to-diameter ratio 15, pH value 7.5; The short glass fiber 10 of monfil diameter 11 μm, length 4.5mm, talcum powder master batch 5, trimeric cyanamide 1, Hinered phenols antioxidant 245 0.5, composite lubricant 0.5, oversubscription are fallen apart coating 0.5, silicone 2 and polyoxymethylene 0.5; Wherein composite lubricant is with the two stearic acid amide of calcium stearate, stearic acid direactive glyceride and ethylene according to 1:2:4 proportions, and oversubscription falls apart coating by organo-siloxane class coupling agent and titante coupling agent and aluminate coupling agent and white oil according to 4:1:3:2 ratio mixed preparing.
embodiment 6
The high temperature resistant polyformaldehyde composite material of a kind of Halogen low warpage type, is made up of the raw material of following weight part: mass flow rate is the coal-based copolymerized methanal 68 of 0.8g/min; The fibrous wollastonite 18 of particle diameter 10 ~ 30 μm, length-to-diameter ratio 14, pH value 7.8; The short glass fiber 12 of monfil diameter 9 μm, length 3.5mm, talcum powder master batch 5, trimeric cyanamide 1, Hinered phenols antioxidant 1,010 0.5, composite lubricant 0.5, oversubscription are fallen apart coating 0.5, silicone 2 and polyoxymethylene 0.5; Wherein composite lubricant is with the two stearic acid amide of calcium stearate, stearic acid direactive glyceride and ethylene according to 1:2:4 proportions, and oversubscription falls apart coating by organo-siloxane class coupling agent and titante coupling agent and aluminate coupling agent and white oil according to 4:1:1:4 ratio mixed preparing.
embodiment 7
The high temperature resistant polyformaldehyde composite material of a kind of Halogen low warpage type, is made up of the raw material of following weight part: mass flow rate is the coal-based copolymerized methanal 68 of 0.8g/min; The fibrous wollastonite 18 of particle diameter 10 ~ 30 μm, length-to-diameter ratio 14, pH value 7.8; The short glass fiber 13 of monfil diameter 9 μm, length 3.5mm, talcum powder master batch 5, trimeric cyanamide 1, Hinered phenols antioxidant 1,010 0.5, composite lubricant 0.5, oversubscription are fallen apart coating 0.5, silicone 2 and polyoxymethylene 0.5; Wherein composite lubricant is with the two stearic acid amide of calcium stearate, stearic acid direactive glyceride and ethylene according to 3:2:5 proportions, and oversubscription falls apart coating by organo-siloxane class coupling agent and titante coupling agent and aluminate coupling agent and white oil according to 4:1:1:5 ratio mixed preparing.
embodiment 8
The high temperature resistant polyformaldehyde composite material of a kind of Halogen low warpage type, is made up of the raw material of following weight part: mass flow rate is the coal-based copolymerized methanal 68 of 0.8g/min; The fibrous wollastonite 18 of particle diameter 10 ~ 30 μm, length-to-diameter ratio 14, pH value 7.8; The short glass fiber 15 of monfil diameter 9 μm, length 3.5mm, talcum powder master batch 5, trimeric cyanamide 1, Hinered phenols antioxidant 1,010 0.5, composite lubricant 0.5, oversubscription are fallen apart coating 0.5, silicone 2 and polyoxymethylene 0.5; Wherein composite lubricant is with the two stearic acid amide of calcium stearate, stearic acid direactive glyceride and ethylene according to 2:2:3 proportions, and oversubscription falls apart coating by organo-siloxane class coupling agent and titante coupling agent and aluminate coupling agent and white oil according to 3:1:1:2 ratio mixed preparing.
embodiment 9
The high temperature resistant polyformaldehyde composite material of a kind of Halogen low warpage type, is made up of the raw material of following weight part: mass flow rate is the coal-based copolymerized methanal 72 of 1.0g/min; The fibrous wollastonite 18 of particle diameter 10 ~ 30 μm, length-to-diameter ratio 11, pH value 7.4; The short glass fiber 16 of monfil diameter 9 μm, length 3.5mm, talcum powder master batch 10, trimeric cyanamide 1, Hinered phenols antioxidant 1,010 0.5, composite lubricant 0.5, oversubscription are fallen apart coating 0.5, silicone 2 and polyoxymethylene 0.5; Wherein composite lubricant is with the two stearic acid amide of calcium stearate, stearic acid direactive glyceride and ethylene according to 1:2:4 proportions, and oversubscription falls apart coating by organo-siloxane class coupling agent and titante coupling agent and aluminate coupling agent and white oil according to 2:1:1:2 ratio mixed preparing.
embodiment 10
The high temperature resistant polyformaldehyde composite material of a kind of Halogen low warpage type, is made up of the raw material of following weight part: mass flow rate is the coal-based copolymerized methanal 62 of 1.2g/min; The fibrous wollastonite 22 of particle diameter 10 ~ 30 μm, length-to-diameter ratio 12, pH value 7.3; The short glass fiber 18 of monfil diameter 10 μm, length 3.5mm, talcum powder master batch 9, trimeric cyanamide 1, Hinered phenols antioxidant 245 0.5, composite lubricant 0.6, oversubscription are fallen apart coating 1.2, silicone 1.7 and polyoxymethylene 0.5; Wherein composite lubricant is with the two stearic acid amide of calcium stearate, stearic acid direactive glyceride and ethylene according to 1:2:3 proportions, and oversubscription falls apart coating by organo-siloxane class coupling agent and titante coupling agent and aluminate coupling agent and white oil according to 4:1:1:2 ratio mixed preparing.
embodiment 11
The high temperature resistant polyformaldehyde composite material of a kind of Halogen low warpage type, is made up of the raw material of following weight part: mass flow rate is the coal-based copolymerized methanal 70 of 1.4g/min; The fibrous wollastonite 18 of particle diameter 10 ~ 30 μm, length-to-diameter ratio 14, pH value 7.8; The short glass fiber 14 of monfil diameter 9 μm, length 3.5mm, talcum powder master batch 5, trimeric cyanamide 1, Hinered phenols antioxidant 1,010 0.5, composite lubricant 0.5, oversubscription are fallen apart coating 0.5, silicone 2 and polyoxymethylene 0.5; Wherein composite lubricant is with the two stearic acid amide of calcium stearate, stearic acid direactive glyceride and ethylene according to 1:2:4 proportions, and oversubscription falls apart coating by organo-siloxane class coupling agent and titante coupling agent and aluminate coupling agent and white oil according to 4:3:1:2 ratio mixed preparing.
embodiment 12
The high temperature resistant polyformaldehyde composite material of a kind of Halogen low warpage type, is made up of the raw material of following weight part: mass flow rate is the coal-based copolymerized methanal 68 of 1.6g/min; The fibrous wollastonite 18 of particle diameter 10 ~ 30 μm, length-to-diameter ratio 16, pH value 7.8; The short glass fiber 17 of monfil diameter 9 μm, length 5mm, talcum powder master batch 8, trimeric cyanamide 1, Hinered phenols antioxidant 1,010 0.5, composite lubricant 0.5, oversubscription are fallen apart coating 0.5, silicone 2 and polyoxymethylene 0.5; Wherein composite lubricant is with the two stearic acid amide of calcium stearate, stearic acid direactive glyceride and ethylene according to 1:2:4 proportions, and oversubscription falls apart coating by organo-siloxane class coupling agent and titante coupling agent and aluminate coupling agent and white oil according to 4:4:1:2 ratio mixed preparing.
embodiment 13
The high temperature resistant polyformaldehyde composite material of a kind of Halogen low warpage type, is made up of the raw material of following weight part: mass flow rate is the coal-based copolymerized methanal 71 of 1.8g/min; The fibrous wollastonite 20 of particle diameter 10 ~ 30 μm, length-to-diameter ratio 18, pH value 7.4; The short glass fiber 10 of monfil diameter 10 μm, length 4.5mm, talcum powder master batch 7, trimeric cyanamide 1, Hinered phenols antioxidant 1,010 0.5, composite lubricant 0.5, oversubscription are fallen apart coating 1.5, silicone 1 and polyoxymethylene 0.3; Wherein composite lubricant is with the two stearic acid amide of calcium stearate, stearic acid direactive glyceride and ethylene according to 1:3:5 proportions, and oversubscription falls apart coating by organo-siloxane class coupling agent and titante coupling agent and aluminate coupling agent and white oil according to 3:2:1:2 ratio mixed preparing.
embodiment 14
The high temperature resistant polyformaldehyde composite material of a kind of Halogen low warpage type, is made up of the raw material of following weight part: mass flow rate is the coal-based copolymerized methanal 76 of 2.0g/min; The fibrous wollastonite 18 of particle diameter 10 ~ 30 μm, length-to-diameter ratio 20, pH value 7.2; The short glass fiber 19 of monfil diameter 9 μm, length 4.5mm, talcum powder master batch 6, trimeric cyanamide 1.3, Hinered phenols antioxidant 245 0.5, composite lubricant 1.5, oversubscription are fallen apart coating 0.3, silicone 2 and polyoxymethylene 0.5; Wherein composite lubricant is with the two stearic acid amide of calcium stearate, stearic acid direactive glyceride and ethylene according to 1:4:4 proportions, and oversubscription falls apart coating by organo-siloxane class coupling agent and titante coupling agent and aluminate coupling agent and white oil according to 4:1:1:2 ratio mixed preparing.
embodiment 15
The high temperature resistant polyformaldehyde composite material of a kind of Halogen low warpage type, is made up of the raw material of following weight part: mass flow rate is the coal-based copolymerized methanal 74 of 2.1g/min; The fibrous wollastonite 14 of particle diameter 10 ~ 30 μm, length-to-diameter ratio 12, pH value 7.5; The short glass fiber 20 of monfil diameter 12 μm, length 2.5mm, talcum powder master batch 5, trimeric cyanamide 1.8, Hinered phenols antioxidant 1,010 0.5, composite lubricant 0.8, oversubscription are fallen apart coating 0.5, silicone 2 and polyoxymethylene 0.5; Wherein composite lubricant is with the two stearic acid amide of calcium stearate, stearic acid direactive glyceride and ethylene according to 3:2:4 proportions, and oversubscription falls apart coating by organo-siloxane class coupling agent and titante coupling agent and aluminate coupling agent and white oil according to 4:1:1:2 ratio mixed preparing.
embodiment 16
The high temperature resistant polyformaldehyde composite material of a kind of Halogen low warpage type, is made up of the raw material of following weight part: mass flow rate is the coal-based copolymerized methanal 61 of 2.3g/min; The fibrous wollastonite 24 of particle diameter 10 ~ 30 μm, length-to-diameter ratio 14, pH value 7.8; The short glass fiber 18 of monfil diameter 9 μm, length 3.5mm, talcum powder master batch 4, trimeric cyanamide 1.7, Hinered phenols antioxidant 245 1.0, composite lubricant 0.6, oversubscription are fallen apart coating 1.1, silicone 2 and polyoxymethylene 0.5; Wherein composite lubricant is with the two stearic acid amide of calcium stearate, stearic acid direactive glyceride and ethylene according to 1:2:4 proportions, and oversubscription falls apart coating by organo-siloxane class coupling agent and titante coupling agent and aluminate coupling agent and white oil according to 4:3:1:2 ratio mixed preparing.
embodiment 17
The high temperature resistant polyformaldehyde composite material of a kind of Halogen low warpage type, is made up of the raw material of following weight part: mass flow rate is the coal-based copolymerized methanal 79 of 0.8g/min; The fibrous wollastonite 13 of particle diameter 10 ~ 30 μm, length-to-diameter ratio 17, pH value 7.3; The short glass fiber 12 of monfil diameter 9 μm, length 3.5mm, talcum powder master batch 3, trimeric cyanamide 1.6, Hinered phenols antioxidant 1,010 0.7, composite lubricant 0.5, oversubscription are fallen apart coating 1.2, silicone 2 and polyoxymethylene 0.5; Wherein composite lubricant is with the two stearic acid amide of calcium stearate, stearic acid direactive glyceride and ethylene according to 1:2:5 proportions, and oversubscription falls apart coating by organo-siloxane class coupling agent and titante coupling agent and aluminate coupling agent and white oil according to 4:1:3:2 ratio mixed preparing.
embodiment 18
The high temperature resistant polyformaldehyde composite material of a kind of Halogen low warpage type, is made up of the raw material of following weight part: mass flow rate is the coal-based copolymerized methanal 68 of 1.5g/min; The fibrous wollastonite 22 of particle diameter 10 ~ 30 μm, length-to-diameter ratio 14, pH value 7.8; The short glass fiber 13 of monfil diameter 9 μm, length 3.5mm, talcum powder master batch 5, trimeric cyanamide 0.9, Hinered phenols antioxidant 1,010 0.6, composite lubricant 0.4, oversubscription are fallen apart coating 1.5, silicone 2 and polyoxymethylene 0.5; Wherein composite lubricant is with the two stearic acid amide of calcium stearate, stearic acid direactive glyceride and ethylene according to 1:2:4 proportions, and oversubscription falls apart coating by organo-siloxane class coupling agent and titante coupling agent and aluminate coupling agent and white oil according to 4:1:1:2 ratio mixed preparing.
embodiment 19
The high temperature resistant polyformaldehyde composite material of a kind of Halogen low warpage type, is made up of the raw material of following weight part: mass flow rate is the coal-based copolymerized methanal 65 of 1.9g/min; The fibrous wollastonite 19 of particle diameter 10 ~ 30 μm, length-to-diameter ratio 17, pH value 7.4; The short glass fiber 12 of monfil diameter 9 μm, length 3.5mm, talcum powder master batch 5, trimeric cyanamide 1.4, Hinered phenols antioxidant 1,010 0.4, composite lubricant 0.5, oversubscription are fallen apart coating 0.5, silicone 2 and polyoxymethylene 0.5; Wherein composite lubricant is with the two stearic acid amide of calcium stearate, stearic acid direactive glyceride and ethylene according to 1:2:4 proportions, and oversubscription falls apart coating by organo-siloxane class coupling agent and titante coupling agent and aluminate coupling agent and white oil according to 4:1:1:2 ratio mixed preparing.
embodiment 20
The high temperature resistant polyformaldehyde composite material of a kind of Halogen low warpage type, is made up of the raw material of following weight part: mass flow rate is the coal-based copolymerized methanal 63 of 1.8g/min; The fibrous wollastonite 23 of particle diameter 10 ~ 30 μm, length-to-diameter ratio 11, pH value 7.7; The short glass fiber 13 of monfil diameter 12 μm, length 3mm, talcum powder master batch 4, trimeric cyanamide 1.3, Hinered phenols antioxidant 245 0.3, composite lubricant 0.5, oversubscription are fallen apart coating 0.5, silicone 2 and polyoxymethylene 0.5; Wherein composite lubricant is with the two stearic acid amide of calcium stearate, stearic acid direactive glyceride and ethylene according to 3:2:4 proportions, and oversubscription falls apart coating by organo-siloxane class coupling agent and titante coupling agent and aluminate coupling agent and white oil according to 2:1:1:2 ratio mixed preparing.
Any one of embodiment 1 ~ 20 preparation technology used is:
(1) dried material: first by polyoxymethylene dehumidification system, raw material polyoxymethylene is carried out drying and processing, bake out temperature 70 DEG C, drying time 3h; Then the polyoxymethylene after oven dry is delivered to polyoxymethylene storage tank through blast system;
(2) mixture auxiliary agent: a. is 20 DEG C in temperature and takes the polyoxymethylene that processed through step (1) and the oversubscription coating that falls apart according to above-mentioned formula and put into mixing machine and stir, churning time 5min, stirring velocity 150r/min; B. be 20 DEG C in temperature according to above-mentioned formula, talcum powder master batch, oxidation inhibitor, composite lubricant, formaldehyde absorbent and other auxiliary addition agents to be put into mixing machine and be uniformly mixed, churning time 10min, stirring velocity 200r/min; Discharge after mixing and drop into addition agent storage tank;
(3) storehouse on auxiliary material: wollastonite is dropped into another addition agent storage tank according to above-mentioned formula, drops into position, side material storage tank according to above-mentioned formula by short glass fiber;
(4) extruding pelletization: each stock material enters high-speed mixer respectively through metering feeding and mixes except the feeding of side, then open side feeding storage tank low speed melt blending in twin screw side feeding machine metering feeding is in the screw combinations situation of twin screw extruder in moderate shear intensity is extruded, forcing machine each section of temperature is respectively: first paragraph 160 ~ 165 DEG C, second segment 165 ~ 170 DEG C, 3rd section 165 ~ 170 DEG C, 4th section 170 ~ 175 DEG C, 5th section 170 ~ 175 DEG C, 6th section 175 ~ 180 DEG C, 7th section 180 ~ 190 DEG C, 8th section 170 ~ 175 DEG C, 9th section 160 ~ 165 DEG C, head temperature is 165 ~ 175 DEG C, screw speed is 300r/min, side feeding is between the 6th section and the 7th section, screw combinations has gear block and toothed disc, water cooling bracing pelletizing, temperature of cooling water 40 ~ 50 DEG C,
(5) dry packing: utilize temperature to be that the hot blast of 80 ~ 100 DEG C carries out backmixing drying, after after bolting the obtained high temperature resistant polyformaldehyde composite material of Halogen low warpage type be delivered to and wait storage tank of feeding; Finished goods warehouse is delivered to finally by metering packing.
By the high temperature resistant polyformaldehyde composite material of low for Halogen of the present invention warpage type by universal testing machine, shock-testing machine etc., the recipe ingredient of research different-shape different ratio is on the impact of the high temperature resistant polyformaldehyde composite material mechanical property of Halogen low warpage type; By heat-drawn wire tester, microcaloire softening temperature tester, differential scanning calorimeter (DSC) and thermogravimetric analyzer (TG) test analysis recipe ingredient on the impact of the high temperature resistant polyformaldehyde composite material thermal characteristics of Halogen low warpage type; By infrared spectra and scanning electron microscope, analyze recipe ingredient to the impact of the high temperature resistant polyformaldehyde composite material microtexture of Halogen low warpage type.
The performance test results of embodiment 1 ~ 20 is in table 1:
Table 1 the performance test results
Claims (10)
1. the high temperature resistant polyformaldehyde composite material of Halogen low warpage type, it is characterized in that, be made up of the raw material of following weight part: polyoxymethylene 60 ~ 80, wollastonite 10 ~ 25, short glass fiber 10 ~ 20, talcum powder master batch 2 ~ 10, formaldehyde absorbent 0.2 ~ 2, oxidation inhibitor 0.2 ~ 2, composite lubricant 0.4 ~ 2, oversubscription are fallen apart coating 0.2 ~ 1.5, other auxiliary agents 0.4 ~ 5.
2. the high temperature resistant polyformaldehyde composite material of Halogen according to claim 1 low warpage type, it is characterized in that, described polyoxymethylene 65 ~ 75, wollastonite 10 ~ 20, short glass fiber 10 ~ 15, talcum powder master batch 2 ~ 6, formaldehyde absorbent 0.5 ~ 1, oxidation inhibitor 0.2 ~ 0.8, composite lubricant 0.4 ~ 1, oversubscription are fallen apart coating 0.2 ~ 0.8, other auxiliary agents 1 ~ 3.
3. the high temperature resistant polyformaldehyde composite material of the low warpage of the Halogen according to claims 1 or 2 type, is characterized in that, described polyoxymethylene is coal-based copolymerized methanal, and the mass flow rate of coal-based copolymerized methanal is 0.8 ~ 3g/min; Described wollastonite is the fibrous wollastonite of particle diameter 10 ~ 30 μm, length-to-diameter ratio 10 ~ 20, pH value 7.2 ~ 7.8.
4. the high temperature resistant polyformaldehyde composite material of the low warpage of the Halogen according to claims 1 or 2 type, is characterized in that, described short glass fiber is the glass fibre of monfil diameter 8 ~ 12 μm, length 2 ~ 5mm.
5. the high temperature resistant polyformaldehyde composite material of the low warpage of the Halogen according to claims 1 or 2 type, it is characterized in that, described talcum powder master batch is white no-load build, and talcum powder master batch is selected from the talcum powder master batch of particle diameter 2 ~ 5mm, length-to-diameter ratio 1 ~ 3, pH value 7.2 ~ 7.8.
6. the high temperature resistant polyformaldehyde composite material of the low warpage of the Halogen according to claims 1 or 2 type, is characterized in that, described composite lubricant is the three kinds or more in calcium stearate, stearic acid direactive glyceride, the two stearic acid amide of ethylene and polyethylene wax.
7. the high temperature resistant polyformaldehyde composite material of the low warpage of the Halogen according to claims 1 or 2 type, it is characterized in that, described oversubscription falls apart coating by organo-siloxane class coupling agent and titante coupling agent and aluminate coupling agent and white oil according to 3:0.5 ~ 1:0.5 ~ 1:0 ~ 2 proportions.
8. the high temperature resistant polyformaldehyde composite material of the low warpage of the Halogen according to claims 1 or 2 type, is characterized in that, other auxiliary agents described are made up of the component of following weight part: silicone powder master batch 0.5 ~ 2 part and Nucleating Agent 0.2 ~ 0.5 part.
9. the high temperature resistant polyformaldehyde composite material of Halogen according to claim 8 low warpage type, is characterized in that, described Nucleating Agent is calcium carbonate, talcum powder, diatomite, carbon nanotube or polymeric amide.
10. the preparation method of the high temperature resistant polyformaldehyde composite material of Halogen low warpage type according to any one of claim 1 ~ 9, it is characterized in that: comprise the steps: that (1) is dry: first by polyoxymethylene dehumidification system, raw material polyoxymethylene is carried out drying and processing, bake out temperature 60 ~ 100 DEG C, drying time 2 ~ 4h; Then the polyoxymethylene after oven dry is delivered to polyoxymethylene storage tank through blast system; (2) mixture auxiliary agent: a. is 18 ~ 23 DEG C in temperature and takes the polyoxymethylene that processed through step (1) and the oversubscription coating that falls apart according to above-mentioned formula and put into mixing machine and stir, churning time 3 ~ 5min, stirring velocity 100 ~ 200r/min; B. be 18 ~ 23 DEG C in temperature according to above-mentioned formula, talcum powder master batch, oxidation inhibitor, composite lubricant, formaldehyde absorbent and other auxiliary addition agents to be put into mixing machine and be uniformly mixed, churning time 10 ~ 15min, stirring velocity 150 ~ 300r/min; Discharge after mixing and drop into addition agent storage tank;
(3) storehouse on auxiliary material: wollastonite is dropped into another addition agent storage tank according to above-mentioned formula, drops into position, side material storage tank according to above-mentioned formula by short glass fiber;
(4) extruding pelletization: each stock material enters high-speed mixer respectively through metering feeding and mixes except the feeding of side, then open side feeding storage tank low speed melt blending in twin screw side feeding machine metering feeding is in the screw combinations situation of twin screw extruder in moderate shear intensity is extruded, extrusion temperature 160 ~ 195 DEG C, screw speed 200 ~ 450r/min; Then water cooling bracing pelletizing, temperature of cooling water is 30 ~ 60 DEG C;
(5) dry packing: utilize temperature to be that the hot blast of 80 ~ 100 DEG C carries out backmixing drying, after after bolting the obtained high temperature resistant polyformaldehyde composite material of Halogen low warpage type be delivered to and wait storage tank of feeding; Finished goods warehouse is delivered to finally by metering packing.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107793695A (en) * | 2017-11-03 | 2018-03-13 | 重庆众誉材工科技有限公司 | A kind of glass fiber reinforced acetal resin and preparation method thereof |
| CN110857345A (en) * | 2018-08-24 | 2020-03-03 | 洛阳双瑞橡塑科技有限公司 | Polyolefin-based composite material and preparation method thereof |
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| CN1274377A (en) * | 1998-02-24 | 2000-11-22 | 旭化成工业株式会社 | Polyoxymethylene resin compsn. |
| CN103937148A (en) * | 2014-05-12 | 2014-07-23 | 云南云天化股份有限公司 | Polyformaldehyde resin composition and preparation method thereof |
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2014
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1274377A (en) * | 1998-02-24 | 2000-11-22 | 旭化成工业株式会社 | Polyoxymethylene resin compsn. |
| CN103937148A (en) * | 2014-05-12 | 2014-07-23 | 云南云天化股份有限公司 | Polyformaldehyde resin composition and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107793695A (en) * | 2017-11-03 | 2018-03-13 | 重庆众誉材工科技有限公司 | A kind of glass fiber reinforced acetal resin and preparation method thereof |
| CN110857345A (en) * | 2018-08-24 | 2020-03-03 | 洛阳双瑞橡塑科技有限公司 | Polyolefin-based composite material and preparation method thereof |
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