CN104341712B - Halogen low warpage high temperature resistant polyformaldehyde composite material of type and preparation method thereof - Google Patents
Halogen low warpage high temperature resistant polyformaldehyde composite material of type and preparation method thereof Download PDFInfo
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- CN104341712B CN104341712B CN201410581526.3A CN201410581526A CN104341712B CN 104341712 B CN104341712 B CN 104341712B CN 201410581526 A CN201410581526 A CN 201410581526A CN 104341712 B CN104341712 B CN 104341712B
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Abstract
The present invention relates to a kind of Halogen low warpage high temperature resistant polyformaldehyde composite material of type, be made up of the raw material of following weight portion: polyformaldehyde 60～80, wollastonite 10～25, short glass fiber 10～20, Pulvis Talci master batch 2～10, formaldehyde absorbent 0.2～2, antioxidant 0.2～2, compounding lubricant 0.4～2, ultra-dispersed covering 0.2～1.5, other auxiliary agents 0.4～5.The Material shrinkage prepared by the inventive method is uniform, and dimensional accuracy is high, and product surface is smooth, highly polished.
Description
Technical field
The invention belongs to technical field of plastic, be specifically related to a kind of Halogen low warpage type high temperature resistant polyformaldehyde composite wood
Material and preparation method thereof.
Background technology
Polyformaldehyde (POM) is a kind of linear thermoplastic polymer not having the high density of side chain, high crystalline, has uniqueness
Mechanical property and preferable self lubricity, coefficient of friction is little and abrasion performance, has excellent water-resistance and corrosion resistant that water absorption rate is low, good
Erosion and self-lubricating and creep-resistant property, particularly have prominent fatigue performance, dimensional stability and excellent electrical property and
Low temperature resistant feature, can (-40～100 DEG C) keep it to be had within the scope of wider temperature mechanics, chemically and electrically etc.
Performance.
Polyformaldehyde (POM) is as a kind of new type chemical material, and annual production is only second to nylon (PA) and Merlon (PC)；It is
The preferable engineering plastics of the nonferrous metal and alloy goods such as alternative metals, particularly copper, aluminum, zinc, be widely used in machine-building,
The traditional field such as electronic apparatus, precision instrument and daily necessities, currently constantly to the emerging neck such as Aero-Space, auto industry
Territory strides forward, but due to POM degree of crystallinity higher (typically up to 70%～85%), spherocrystal crystal grain is relatively big, and notch sensitivity is big, breach
The performance deficiencies such as impact strength is relatively low, poor heat resistance, easy firing strongly limit the application of polyformaldehyde (POM).
Polyformaldehyde (POM) is uniquely not rely on crude oil in engineering plastics, with Coal Chemical Industry product methanol as raw material, with shorter
Technological process, the kind that can manufacture in a large number, be extremely important C-1 chemistry downstream product in Coal Chemical Industry product chain, development is poly-
Formaldehyde and downstream industry thereof meet the energy national conditions of China's few gas of oil-poor rich coal, have important strategic importance.
Polyformaldehyde (POM) is although market demand at home is relatively big, but its research, development and production are still in starting
Stage, yield and performance are far from meeting the market demand；And high-performance modified polyformaldehyde product, then basic dependence on import or by
The large multinational company of domestic individual proprietorship is controlled.Therefore carry out polyoxymethylene modified research, improve the property of polyformaldehyde product further
Energy and quality, improve its added value and the market competitiveness, can meet the individual demand of different user, promotes the high property of product
Energyization, become more meticulous, differential and systematization, not only the extension to polyformaldehyde (POM) application market is particularly important, simultaneously to poly-first
The technological progress of aldehyde (POM) industry is extremely advantageous, the most crucial to improving the domestic polyformaldehyde manufacturing enterprise market competitiveness.
Summary of the invention
It is an object of the invention to overcome existing technological deficiency to provide a kind of Halogen low warpage high temperature resistant polyformaldehyde of type
Composite, effectively solve bigger internal stress that crystalline materials polyformaldehyde (POM) produces in forming process due to self and
The product buckling deformation, the dimensional accuracy that cause are the highest, product surface out-of-flatness, fineness are the highest, use temperature conditions to require height
Etc. problem.
In order to achieve the above object, the present invention adopts the following technical scheme that
The present invention provides a kind of Halogen low warpage high temperature resistant polyformaldehyde composite material of type, by the raw material system of following weight portion
Become: polyformaldehyde 60～80, wollastonite 10～25, short glass fiber 10～20, Pulvis Talci master batch 2～10, formaldehyde absorbent
0.2～2, antioxidant 0.2～2, compounding lubricant 0.4～2, ultra-dispersed covering 0.2～1.5, other auxiliary agents 0.4～5.
The Halogen low warpage high temperature resistant polyformaldehyde composite material of type, is made up of the raw material of following weight portion: polyformaldehyde 65～75,
Wollastonite 10～20, short glass fiber 10～15, Pulvis Talci master batch 2～6, formaldehyde absorbent 0.5～1, antioxidant 0.2～
0.8, compounding lubricant 0.4～1, ultra-dispersed covering 0.2～0.8, other auxiliary agents 1～3.
Described polyformaldehyde is coal base copolymerized methanal, and the mass flow rate of coal base copolymerized methanal is 0.8～3g/min.
Described wollastonite is particle diameter 10～30 μm, draw ratio 10～20, the fibrous wollastonite of pH value 7.2～7.8.
Described short glass fiber is monfil diameter 8～12 μm, the glass fibre of length 2～5mm.
Described Pulvis Talci master batch is white no-load build, and Pulvis Talci master batch is selected from particle diameter 2～5mm, draw ratio 1～3, pH value
The Pulvis Talci master batch of 7.2～7.8.
Described compounding lubricant is by calcium stearate, stearic acid monoglyceride, the double stearic acid amides (TAF) of ethylene and poly-second
Three kinds or more in alkene wax, wherein with the double stearic acid amide (TAF) of calcium stearate, stearic acid monoglyceride and ethylene according to
1:2:4 is optimum.
Described ultra-dispersed covering is by organosiloxane class coupling agent and titante coupling agent and aluminate coupling
Agent and white oil are 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 portion: 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, Pulvis Talci, kieselguhr, it is also possible to selects
The organic nucleating agents such as CNT, polyamide, acefal homopolymer.
The preparation method of the Halogen low warpage high temperature resistant polyformaldehyde composite material of type, comprises the steps: (1) dried material:
First pass through polyformaldehyde drying system and raw material polyformaldehyde is carried out drying and processing, drying temperature 60～100 DEG C, drying time 2～4h；
Then the polyformaldehyde after drying delivers to polyformaldehyde storage tank through blast system；
(2) mixture auxiliary agent: a. is 18～23 DEG C in temperature and weighs the poly-first processed through step (1) according to above-mentioned formula
Aldehyde and ultra-dispersed covering are put in mixer and are stirred, mixing time 3～5min, mixing speed 100～200r/min；B. in
Temperature be 18～23 DEG C according to above-mentioned formula by Pulvis Talci master batch, antioxidant, compounding lubricant, formaldehyde absorbent and other auxiliary
Auxiliary agent puts into mixer stirring mixing, mixing time 10～15min, mixing speed 150～300r/min；Discharge after mixing and put into
Addition agent storage tank；
(3) storehouse on adjuvant: according to above-mentioned formula, wollastonite is put into another addition agent storage tank, according to above-mentioned formula by chopped glass
Glass fiber puts into position, side material storage tank；
(4) extruding pelletization: each stock material mixes respectively through metering feeding entrance high-speed mixer in addition to the feeding of side,
Then open side feeding storage tank through twin screw side feeding machine metering feeding through double screw extruder at the spiral shell of moderate shear intensity
Low speed melt blending extrusion, extrusion temperature 160～195 DEG C, screw speed 200～450r/min under bar combined situation；Then
Water cooling bracing pelletizing, cooling water temperature is 30～60 DEG C；
(5) dry packing: the hot blast utilizing temperature to be 80～100 DEG C carries out backmixing and is dried, after through Vibration Screen
Prepare the Halogen low warpage high temperature resistant polyformaldehyde composite material of type after Fen and be delivered to storage tank to be fed；It is delivered to through metering packing after
Finished room.
Described short glass fiber is by organosiloxane class coupling agent and titante coupling agent and/aluminate coupling
The mixed solvent that agent configures according to a certain ratio carries out surface infiltration process, obtains monfil a diameter of 8～12 μm, a length of
The glass fibre of 2～5mm.
Described antioxidant is Hinered phenols antioxidant 245 or Hinered phenols antioxidant 1010.
Described formaldehyde absorbent is tripolycyanamide.
Compared with prior art, the invention have the advantage that
(1) the Halogen low warpage high temperature resistant polyformaldehyde composite material of type that the present invention obtains, shrinks uniformly, and dimensional accuracy is high,
Product surface is smooth, highly polished；Molding shrinkage≤1.0, load heat distortion temperature (1.8MPa) >=150 DEG C, initial heat point
Solve temperature >=410 DEG C, yield stress >=80MPa, bending strength >=110MPa, be suitable for manufacturing low warpage, high temperature resistant, high
The Polyformaldehyde product that the different performances such as intensity require.
(2) preparation method of the high temperature resistant polyformaldehyde composite material of Halogen of the present invention low warpage type makes the microstructure of material relatively
Stable, interface cohesion degree is higher, and apparent property is superior, anisotropy that lightening material orientation causes and causing because of crystallization
Ununiform shrinkage, thus reduce the warpage degree of polyformaldehyde, moulding shrink uniformity coefficient meet its use requirement.
(3) present invention efficiently solves crystalline materials polyformaldehyde (POM) in forming process owing to self produces relatively
Big internal stress and the product buckling deformation that causes, improve the dimensional accuracy of polyformaldehyde product and shrink uniformity, improve poly-
The heat stability of formaldehyde products so meet polyformaldehyde product under higher temperature conditions, dimension precision requirement is high, surface is put down
Whole degree smoothness requirements is high, the use requirement of part industry goods material Halogen, also will be for widening polyformaldehyde (POM) further
Application, it is achieved the practical target of general-purpose plastics through engineering approaches, engineering plastics functionalization and special engineering plastics plays very well
Impetus.
Detailed description of the invention
Below in conjunction with example, technical scheme is further described, but described is only embodied as example
For explaining the present invention and in for limiting the scope of the present invention.
The source of chemical reagent:
Polyformaldehyde Kaifeng Long Yu Chemical Co., Ltd. produces, MC90 type
Wollastonite Jiangxi global wollastonite fibre Materials Co., Ltd produces
Short glass fiber Jushi Group Co., Ltd. produces, ECS11-4.5-500 type
Other chemical reagent is commercially available
Embodiment 1
A kind of Halogen low warpage high temperature resistant polyformaldehyde composite material of type, is made up of the raw material of following weight portion: mass flow
Speed is 0.95g/min coal base copolymerized methanal 65；Particle diameter 10～30 μm, draw ratio 11, the fibrous wollastonite 15 of pH value 7.5；
Monfil diameter 11 μm, the short glass fiber 10 of length 4.5mm, Pulvis Talci master batch 5, tripolycyanamide 1, Hinered phenols are anti-
Oxygen agent 1,010 0.5, compounding lubricant 0.5, ultra-dispersed covering 0.5, silicone 2 and polyformaldehyde 0.5；Wherein compound lubricant
With the double stearic acid amide of calcium stearate, stearic acid monoglyceride and ethylene according to 1:2:4 proportions, ultra-dispersed covering is by having
Organic siloxane class coupling agent and titante coupling agent and aluminate coupling agent and white oil mix according to 4:1:1:2 ratio and join
System.
Embodiment 2
A kind of Halogen low warpage high temperature resistant polyformaldehyde composite material of type, is made up of the raw material of following weight portion: mass flow
Speed is 0.95g/min coal base copolymerized methanal 70；Particle diameter 10～30 μm, draw ratio 12, the fibrous wollastonite 10 of pH value 7.2；
Monfil diameter 11 μm, the short glass fiber 10 of length 4.5mm, Pulvis Talci master batch 5, tripolycyanamide 1, Hinered phenols are anti-
Oxygen agent 1,010 0.5, compounding lubricant 0.5, ultra-dispersed covering 0.5, silicone 2 and polyformaldehyde 0.5；Wherein compound lubricant
With the double stearic acid amide of calcium stearate, stearic acid monoglyceride and ethylene according to 1:2:4 proportions, ultra-dispersed covering is by having
Organic siloxane class coupling agent and titante coupling agent and aluminate coupling agent and white oil mix according to 4:2:1:2 ratio and join
System.
Embodiment 3
A kind of Halogen low warpage high temperature resistant polyformaldehyde composite material of type, is made up of the raw material of following weight portion: mass flow
Speed is 0.95g/min coal base copolymerized methanal 65；Particle diameter 10～30 μm, draw ratio 10, the fibrous wollastonite 20 of pH value 7.3；
Monfil diameter 11 μm, the short glass fiber 15 of length 4.5mm, Pulvis Talci master batch 5, tripolycyanamide 1, Hinered phenols are anti-
Oxygen agent 1,010 0.5, compounding lubricant 0.5, ultra-dispersed covering 0.5, silicone 2 and polyformaldehyde 0.5；Wherein compound lubricant
With calcium stearate, stearic acid monoglyceride and Tissuemat E according to 1:2:4 proportions, ultra-dispersed covering is by organosiloxane
Class coupling agent and titante coupling agent and aluminate coupling agent and white oil are according to 4:1:1:2 ratio mixed preparing.
Embodiment 4
A kind of Halogen low warpage high temperature resistant polyformaldehyde composite material of type, is made up of the raw material of following weight portion: mass flow
Speed is 0.95g/min coal base copolymerized methanal 65；Particle diameter 10～30 μm, draw ratio 12, the fibrous wollastonite 10 of pH value 7.4；
Monfil diameter 11 μm, the short glass fiber 15 of length 4.5mm, Pulvis Talci master batch 5, tripolycyanamide 1, Hinered phenols are anti-
Oxygen agent 245 0.5, compounding lubricant 0.5, ultra-dispersed covering 0.5, silicone 2 and polyformaldehyde 0.5；Wherein compound lubricant with
Calcium stearate, stearic acid monoglyceride: the double stearic acid amide of ethylene: Tissuemat E is according to 1:2:4:3 proportions, oversubscription Bales Off
Cover agent by organosiloxane class coupling agent and titante coupling agent and aluminate coupling agent and white oil according to 4:1:1:2 ratio
Example mixed preparing.
Embodiment 5
A kind of Halogen low warpage high temperature resistant polyformaldehyde composite material of type, is made up of the raw material of following weight portion: mass flow
Speed is 0.95g/min coal base copolymerized methanal 70；Particle diameter 10～30 μm, draw ratio 15, the fibrous wollastonite 15 of pH value 7.5；
Monfil diameter 11 μm, the short glass fiber 10 of length 4.5mm, Pulvis Talci master batch 5, tripolycyanamide 1, Hinered phenols antioxygen
Agent 245 0.5, compounding lubricant 0.5, ultra-dispersed covering 0.5, silicone 2 and polyformaldehyde 0.5；Wherein compound lubricant with firmly
The double stearic acid amide of fat acid calcium, stearic acid monoglyceride and ethylene is according to 1:2:4 proportions, and ultra-dispersed covering is by organosilicon
Oxygen alkanes coupling agent and titante coupling agent and aluminate coupling agent and white oil are according to 4:1:3:2 ratio mixed preparing.
Embodiment 6
A kind of Halogen low warpage high temperature resistant polyformaldehyde composite material of type, is made up of the raw material of following weight portion: mass flow
Speed is 0.8g/min coal base copolymerized methanal 68；Particle diameter 10～30 μm, draw ratio 14, the fibrous wollastonite 18 of pH value 7.8；
Monfil diameter 9 μm, the short glass fiber 12 of length 3.5mm, Pulvis Talci master batch 5, tripolycyanamide 1, Hinered phenols antioxygen
Agent 1,010 0.5, compounding lubricant 0.5, ultra-dispersed covering 0.5, silicone 2 and polyformaldehyde 0.5；Wherein compound lubricant with
The double stearic acid amide of calcium stearate, stearic acid monoglyceride and ethylene is according to 1:2:4 proportions, and ultra-dispersed covering is by organic
Type siloxane coupling agent and titante coupling agent and aluminate coupling agent and white oil mix according to 4:1:1:4 ratio and join
System.
Embodiment 7
A kind of Halogen low warpage high temperature resistant polyformaldehyde composite material of type, is made up of the raw material of following weight portion: mass flow
Speed is 0.8g/min coal base copolymerized methanal 68；Particle diameter 10～30 μm, draw ratio 14, the fibrous wollastonite 18 of pH value 7.8；
Monfil diameter 9 μm, the short glass fiber 13 of length 3.5mm, Pulvis Talci master batch 5, tripolycyanamide 1, Hinered phenols antioxygen
Agent 1,010 0.5, compounding lubricant 0.5, ultra-dispersed covering 0.5, silicone 2 and polyformaldehyde 0.5；Wherein compound lubricant with
The double stearic acid amide of calcium stearate, stearic acid monoglyceride and ethylene is according to 3:2:5 proportions, and ultra-dispersed covering is by organic
Type siloxane coupling agent and titante coupling agent and aluminate coupling agent and white oil mix according to 4:1:1:5 ratio and join
System.
Embodiment 8
A kind of Halogen low warpage high temperature resistant polyformaldehyde composite material of type, is made up of the raw material of following weight portion: mass flow
Speed is 0.8g/min coal base copolymerized methanal 68；Particle diameter 10～30 μm, draw ratio 14, the fibrous wollastonite 18 of pH value 7.8；
Monfil diameter 9 μm, the short glass fiber 15 of length 3.5mm, Pulvis Talci master batch 5, tripolycyanamide 1, Hinered phenols antioxygen
Agent 1,010 0.5, compounding lubricant 0.5, ultra-dispersed covering 0.5, silicone 2 and polyformaldehyde 0.5；Wherein compound lubricant with
The double stearic acid amide of calcium stearate, stearic acid monoglyceride and ethylene is according to 2:2:3 proportions, and ultra-dispersed covering is by organic
Type siloxane coupling agent and titante coupling agent and aluminate coupling agent and white oil mix according to 3:1:1:2 ratio and join
System.
Embodiment 9
A kind of Halogen low warpage high temperature resistant polyformaldehyde composite material of type, is made up of the raw material of following weight portion: mass flow
Speed is 1.0g/min coal base copolymerized methanal 72；Particle diameter 10～30 μm, draw ratio 11, the fibrous wollastonite 18 of pH value 7.4；
Monfil diameter 9 μm, the short glass fiber 16 of length 3.5mm, Pulvis Talci master batch 10, tripolycyanamide 1, Hinered phenols are anti-
Oxygen agent 1,010 0.5, compounding lubricant 0.5, ultra-dispersed covering 0.5, silicone 2 and polyformaldehyde 0.5；Wherein compound lubricant
With the double stearic acid amide of calcium stearate, stearic acid monoglyceride and ethylene according to 1:2:4 proportions, ultra-dispersed covering is by having
Organic siloxane class coupling agent and titante coupling agent and aluminate coupling agent and white oil mix according to 2:1:1:2 ratio and join
System.
Embodiment 10
A kind of Halogen low warpage high temperature resistant polyformaldehyde composite material of type, is made up of the raw material of following weight portion: mass flow
Speed is 1.2g/min coal base copolymerized methanal 62；Particle diameter 10～30 μm, draw ratio 12, the fibrous wollastonite 22 of pH value 7.3；
Monfil diameter 10 μm, the short glass fiber 18 of length 3.5mm, Pulvis Talci master batch 9, tripolycyanamide 1, Hinered phenols are anti-
Oxygen agent 245 0.5, compounding lubricant 0.6, ultra-dispersed covering 1.2, silicone 1.7 and polyformaldehyde 0.5；Wherein compound lubricant
With the double stearic acid amide of calcium stearate, stearic acid monoglyceride and ethylene according to 1:2:3 proportions, ultra-dispersed covering is by having
Organic siloxane class coupling agent and titante coupling agent and aluminate coupling agent and white oil mix according to 4:1:1:2 ratio and join
System.
Embodiment 11
A kind of Halogen low warpage high temperature resistant polyformaldehyde composite material of type, is made up of the raw material of following weight portion: mass flow
Speed is 1.4g/min coal base copolymerized methanal 70；Particle diameter 10～30 μm, draw ratio 14, the fibrous wollastonite 18 of pH value 7.8；
Monfil diameter 9 μm, the short glass fiber 14 of length 3.5mm, Pulvis Talci master batch 5, tripolycyanamide 1, Hinered phenols antioxygen
Agent 1,010 0.5, compounding lubricant 0.5, ultra-dispersed covering 0.5, silicone 2 and polyformaldehyde 0.5；Wherein compound lubricant with
The double stearic acid amide of calcium stearate, stearic acid monoglyceride and ethylene is according to 1:2:4 proportions, and ultra-dispersed covering is by organic
Type siloxane coupling agent and titante coupling agent and aluminate coupling agent and white oil mix according to 4:3:1:2 ratio and join
System.
Embodiment 12
A kind of Halogen low warpage high temperature resistant polyformaldehyde composite material of type, is made up of the raw material of following weight portion: mass flow
Speed is 1.6g/min coal base copolymerized methanal 68；Particle diameter 10～30 μm, draw ratio 16, the fibrous wollastonite 18 of pH value 7.8；
Monfil diameter 9 μm, the short glass fiber 17 of length 5mm, Pulvis Talci master batch 8, tripolycyanamide 1, Hinered phenols antioxidant
1010 0.5, compounding lubricant 0.5, ultra-dispersed covering 0.5, silicone 2 and polyformaldehyde 0.5；Wherein compound lubricant with firmly
The double stearic acid amide of fat acid calcium, stearic acid monoglyceride and ethylene is according to 1:2:4 proportions, and ultra-dispersed covering is by organosilicon
Oxygen alkanes coupling agent and titante coupling agent and aluminate coupling agent and white oil are according to 4:4:1:2 ratio mixed preparing.
Embodiment 13
A kind of Halogen low warpage high temperature resistant polyformaldehyde composite material of type, is made up of the raw material of following weight portion: mass flow
Speed is 1.8g/min coal base copolymerized methanal 71；Particle diameter 10～30 μm, draw ratio 18, the fibrous wollastonite 20 of pH value 7.4；
Monfil diameter 10 μm, the short glass fiber 10 of length 4.5mm, Pulvis Talci master batch 7, tripolycyanamide 1, Hinered phenols are anti-
Oxygen agent 1,010 0.5, compounding lubricant 0.5, ultra-dispersed covering 1.5, silicone 1 and polyformaldehyde 0.3；Wherein compound lubricant
With the double stearic acid amide of calcium stearate, stearic acid monoglyceride and ethylene according to 1:3:5 proportions, ultra-dispersed covering is by having
Organic siloxane class coupling agent and titante coupling agent and aluminate coupling agent and white oil mix according to 3:2:1:2 ratio and join
System.
Embodiment 14
A kind of Halogen low warpage high temperature resistant polyformaldehyde composite material of type, is made up of the raw material of following weight portion: mass flow
Speed is 2.0g/min coal base copolymerized methanal 76；Particle diameter 10～30 μm, draw ratio 20, the fibrous wollastonite 18 of pH value 7.2；
Monfil diameter 9 μm, the short glass fiber 19 of length 4.5mm, Pulvis Talci master batch 6, tripolycyanamide 1.3, Hinered phenols are anti-
Oxygen agent 245 0.5, compounding lubricant 1.5, ultra-dispersed covering 0.3, silicone 2 and polyformaldehyde 0.5；Wherein compound lubricant with
The double stearic acid amide of calcium stearate, stearic acid monoglyceride and ethylene is according to 1:4:4 proportions, and ultra-dispersed covering is by organic
Type siloxane coupling agent and titante coupling agent and aluminate coupling agent and white oil mix according to 4:1:1:2 ratio and join
System.
Embodiment 15
A kind of Halogen low warpage high temperature resistant polyformaldehyde composite material of type, is made up of the raw material of following weight portion: mass flow
Speed is 2.1g/min coal base copolymerized methanal 74；Particle diameter 10～30 μm, draw ratio 12, the fibrous wollastonite 14 of pH value 7.5；
Monfil diameter 12 μm, the short glass fiber 20 of length 2.5mm, Pulvis Talci master batch 5, tripolycyanamide 1.8, Hinered phenols
Antioxidant 1010 0.5, compounding lubricant 0.8, ultra-dispersed covering 0.5, silicone 2 and polyformaldehyde 0.5；Wherein compounding lubrication
Agent with the double stearic acid amide of calcium stearate, stearic acid monoglyceride and ethylene according to 3:2:4 proportions, ultra-dispersed covering by
Organosiloxane class coupling agent and titante coupling agent and aluminate coupling agent and white oil mix according to 4:1:1:2 ratio
Preparation.
Embodiment 16
A kind of Halogen low warpage high temperature resistant polyformaldehyde composite material of type, is made up of the raw material of following weight portion: mass flow
Speed is 2.3g/min coal base copolymerized methanal 61；Particle diameter 10～30 μm, draw ratio 14, the fibrous wollastonite 24 of pH value 7.8；
Monfil diameter 9 μm, the short glass fiber 18 of length 3.5mm, Pulvis Talci master batch 4, tripolycyanamide 1.7, Hinered phenols are anti-
Oxygen agent 245 1.0, compounding lubricant 0.6, ultra-dispersed covering 1.1, silicone 2 and polyformaldehyde 0.5；Wherein compound lubricant with
The double stearic acid amide of calcium stearate, stearic acid monoglyceride and ethylene is according to 1:2:4 proportions, and ultra-dispersed covering is by organic
Type siloxane coupling agent and titante coupling agent and aluminate coupling agent and white oil mix according to 4:3:1:2 ratio and join
System.
Embodiment 17
A kind of Halogen low warpage high temperature resistant polyformaldehyde composite material of type, is made up of the raw material of following weight portion: mass flow
Speed is 0.8g/min coal base copolymerized methanal 79；Particle diameter 10～30 μm, draw ratio 17, the fibrous wollastonite 13 of pH value 7.3；
Monfil diameter 9 μm, the short glass fiber 12 of length 3.5mm, Pulvis Talci master batch 3, tripolycyanamide 1.6, Hinered phenols are anti-
Oxygen agent 1,010 0.7, compounding lubricant 0.5, ultra-dispersed covering 1.2, silicone 2 and polyformaldehyde 0.5；Wherein compound lubricant
With the double stearic acid amide of calcium stearate, stearic acid monoglyceride and ethylene according to 1:2:5 proportions, ultra-dispersed covering is by having
Organic siloxane class coupling agent and titante coupling agent and aluminate coupling agent and white oil mix according to 4:1:3:2 ratio and join
System.
Embodiment 18
A kind of Halogen low warpage high temperature resistant polyformaldehyde composite material of type, is made up of the raw material of following weight portion: mass flow
Speed is 1.5g/min coal base copolymerized methanal 68；Particle diameter 10～30 μm, draw ratio 14, the fibrous wollastonite 22 of pH value 7.8；
Monfil diameter 9 μm, the short glass fiber 13 of length 3.5mm, Pulvis Talci master batch 5, tripolycyanamide 0.9, Hinered phenols are anti-
Oxygen agent 1,010 0.6, compounding lubricant 0.4, ultra-dispersed covering 1.5, silicone 2 and polyformaldehyde 0.5；Wherein compound lubricant
With the double stearic acid amide of calcium stearate, stearic acid monoglyceride and ethylene according to 1:2:4 proportions, ultra-dispersed covering is by having
Organic siloxane class coupling agent and titante coupling agent and aluminate coupling agent and white oil mix according to 4:1:1:2 ratio and join
System.
Embodiment 19
A kind of Halogen low warpage high temperature resistant polyformaldehyde composite material of type, is made up of the raw material of following weight portion: mass flow
Speed is 1.9g/min coal base copolymerized methanal 65；Particle diameter 10～30 μm, draw ratio 17, the fibrous wollastonite 19 of pH value 7.4；
Monfil diameter 9 μm, the short glass fiber 12 of length 3.5mm, Pulvis Talci master batch 5, tripolycyanamide 1.4, Hinered phenols are anti-
Oxygen agent 1,010 0.4, compounding lubricant 0.5, ultra-dispersed covering 0.5, silicone 2 and polyformaldehyde 0.5；Wherein compound lubricant
With the double stearic acid amide of calcium stearate, stearic acid monoglyceride and ethylene according to 1:2:4 proportions, ultra-dispersed covering is by having
Organic siloxane class coupling agent and titante coupling agent and aluminate coupling agent and white oil mix according to 4:1:1:2 ratio and join
System.
Embodiment 20
A kind of Halogen low warpage high temperature resistant polyformaldehyde composite material of type, is made up of the raw material of following weight portion: mass flow
Speed is 1.8g/min coal base copolymerized methanal 63；Particle diameter 10～30 μm, draw ratio 11, the fibrous wollastonite 23 of pH value 7.7；
Monfil diameter 12 μm, the short glass fiber 13 of length 3mm, Pulvis Talci master batch 4, tripolycyanamide 1.3, Hinered phenols are anti-
Oxygen agent 245 0.3, compounding lubricant 0.5, ultra-dispersed covering 0.5, silicone 2 and polyformaldehyde 0.5；Wherein compound lubricant with
The double stearic acid amide of calcium stearate, stearic acid monoglyceride and ethylene is according to 3:2:4 proportions, and ultra-dispersed covering is by organic
Type siloxane coupling agent and titante coupling agent and aluminate coupling agent and white oil mix according to 2:1:1:2 ratio and join
System.
Preparation technology used by any one of embodiment 1～20 is:
(1) dried material: first pass through polyformaldehyde drying system and raw material polyformaldehyde is carried out drying and processing, dry temperature 70
DEG C, drying time 3h；Then the polyformaldehyde after drying delivers to polyformaldehyde storage tank through blast system；
(2) mixture auxiliary agent: a. in temperature be 20 DEG C according to above-mentioned formula weigh the polyformaldehyde processed through step (1) and
Ultra-dispersed covering is put in mixer and is stirred, mixing time 5min, mixing speed 150r/min；B. in temperature be 20 DEG C by
According to above-mentioned formula, Pulvis Talci master batch, antioxidant, compounding lubricant, formaldehyde absorbent and other auxiliary addition agents are put into mixer and stirred
Mix mixing, mixing time 10min, mixing speed 200r/min；Discharge after mixing and put into addition agent storage tank；
(3) storehouse on adjuvant: according to above-mentioned formula, wollastonite is put into another addition agent storage tank, according to above-mentioned formula by chopped glass
Glass fiber puts into position, side material storage tank；
(4) extruding pelletization: each stock material mixes respectively through metering feeding entrance high-speed mixer in addition to the feeding of side,
Then open side feeding storage tank through twin screw side feeding machine metering feeding through double screw extruder at the spiral shell of moderate shear intensity
Low speed melt blending extrusion under bar combined situation, each section of temperature of extruder is respectively as follows: first paragraph 160～165 DEG C, second segment
165～170 DEG C, the 3rd section 165～170 DEG C, the 4th section 170～175 DEG C, the 5th section 170～175 DEG C, the 6th section 175～180
DEG C, the 7th section 180～190 DEG C, the 8th section 170～175 DEG C, the 9th section 160～165 DEG C, head temperature is 165～175 DEG C, spiral shell
Bar rotating speed is 300r/min, and side feeding is between the 6th section and the 7th section, and screw combinations has gear block and toothed disc, water cooling bracing
Pelletizing, cooling water temperature 40～50 DEG C；
(5) dry packing: the hot blast utilizing temperature to be 80～100 DEG C carries out backmixing and is dried, after through Vibration Screen
Prepare the Halogen low warpage high temperature resistant polyformaldehyde composite material of type after Fen and be delivered to storage tank to be fed；It is delivered to through metering packing after
Finished room.
By low for the Halogen of the present invention high temperature resistant polyformaldehyde composite material of warpage type by universal testing machine, shock machine
Deng, recipe ingredient warpage low to the Halogen type high temperature resistant polyformaldehyde composite material mechanical property of research different-shape different ratio
Impact；By heat distortion temperature tester, microcaloire softening point tester, differential scanning calorimeter (DSC) and thermogravimetric analyzer
(TG) impact of test analysis recipe ingredient warpage low on Halogen type high temperature resistant polyformaldehyde composite material hot property；Pass through infrared light
Spectrum and scanning electron microscope, analyze the impact of recipe ingredient warpage low on Halogen type high temperature resistant polyformaldehyde composite material microstructure.
The performance test results of embodiment 1～20 is shown in Table 1:
Table 1 the performance test results
Claims (8)
1. the Halogen low warpage high temperature resistant polyformaldehyde composite material of type, it is characterised in that be made up of the raw material of following weight portion:
Polyformaldehyde 60～80, wollastonite 10～25, short glass fiber 10～20, Pulvis Talci master batch 2～10, formaldehyde absorbent 0.2
～2, antioxidant 0.2～2, compounding lubricant 0.4～2, ultra-dispersed covering 0.2～1.5, other auxiliary agents 0.4～5；Described multiple
Join lubricant be in calcium stearate, stearic acid monoglyceride, the double stearic acid amide of ethylene and Tissuemat E three kinds or three kinds with
On；Described ultra-dispersed covering be by organosiloxane class coupling agent and titante coupling agent and aluminate coupling agent and
White oil is according to 3:0.5 ~ 1:0.5 ~ 1:0 ~ 2 proportions.
The Halogen the most according to claim 1 low warpage high temperature resistant polyformaldehyde composite material of type, it is characterised in that described poly-first
Aldehyde 65～75, wollastonite 10～20, short glass fiber 10～15, Pulvis Talci master batch 2～6, formaldehyde absorbent 0.5～1, anti-
Oxygen agent 0.2～0.8, compounding lubricant 0.4～1, ultra-dispersed covering 0.2～0.8, other auxiliary agents 1～3.
3. according to the low warpage high temperature resistant polyformaldehyde composite material of type of the Halogen described in claims 1 or 2, it is characterised in that institute
Stating polyformaldehyde is coal base copolymerized methanal, and the mass flow rate of coal base copolymerized methanal is 0.8～3g/min；Described wollastonite is grain
Footpath 10～30 μm, draw ratio 10～20, the fibrous wollastonite of pH value 7.2～7.8.
4. according to the low warpage high temperature resistant polyformaldehyde composite material of type of the Halogen described in claims 1 or 2, it is characterised in that institute
Stating short glass fiber is monfil diameter 8～12 μm, the glass fibre of length 2～5mm.
5. according to the low warpage high temperature resistant polyformaldehyde composite material of type of the Halogen described in claims 1 or 2, it is characterised in that institute
Stating Pulvis Talci master batch for white no-load build, Pulvis Talci master batch is selected from particle diameter 2～5mm, draw ratio 1～3, pH value 7.2～7.8
Pulvis Talci master batch.
6. according to the low warpage high temperature resistant polyformaldehyde composite material of type of the Halogen described in claims 1 or 2, it is characterised in that institute
State other auxiliary agents to be made up of the component of following weight portion: silicone powder master batch 0.5～2 parts and Nucleating Agent 0.2～0.5 part.
The Halogen the most according to claim 6 low warpage high temperature resistant polyformaldehyde composite material of type, it is characterised in that described nucleus
Agent is calcium carbonate, Pulvis Talci, kieselguhr, CNT or polyamide.
8. according to the preparation method of the Halogen low warpage high temperature resistant polyformaldehyde composite material of type described in any one of claim 1～7, its
It is characterised by: comprise the steps: that (1) is dried: first pass through polyformaldehyde drying system and raw material polyformaldehyde is carried out drying and processing, dry
Dry temperature 60～100 DEG C, drying time 2～4h；Then the polyformaldehyde after drying delivers to polyformaldehyde storage tank through blast system；
(2) mixture auxiliary agent: a. is 18～23 DEG C in temperature and weighs the polyformaldehyde and oversubscription processed through step (1) according to above-mentioned formula
Scattered covering is put in mixer and is stirred, mixing time 3～5min, mixing speed 100～200r/min；B. in temperature be 18
～Pulvis Talci master batch, antioxidant, compounding lubricant, formaldehyde absorbent and other auxiliary addition agents put into by 23 DEG C according to above-mentioned formula
Mixer stirring mixing, mixing time 10～15min, mixing speed 150～300r/min；Discharge after mixing and put into auxiliary agent storage
Tank；
(3) storehouse on adjuvant: wollastonite is put into another addition agent storage tank according to above-mentioned formula, according to above-mentioned formula, staple glass is fine
Dimension puts into position, side material storage tank；
(4) extruding pelletization: each stock material mixes, then respectively through metering feeding entrance high-speed mixer in addition to the feeding of side
Open side feeding storage tank through twin screw side feeding machine metering feeding through double screw extruder in the screw rod group of moderate shear intensity
Low speed melt blending extrusion, extrusion temperature 160～195 DEG C, screw speed 200～450r/min in the case of conjunction；Then water-cooled
Tie rod pelletizing, cooling water temperature is 30～60 DEG C；
(5) dry packing: the hot blast utilizing temperature to be 80～100 DEG C carries out backmixing and is dried, after after bolting
Prepare the Halogen low warpage high temperature resistant polyformaldehyde composite material of type and be delivered to storage tank to be fed；It is delivered to finished product through metering packing after
Warehouse.
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