CN109294160A - A kind of polyformaldehyde composite material and preparation method thereof - Google Patents
A kind of polyformaldehyde composite material and preparation method thereof Download PDFInfo
- Publication number
- CN109294160A CN109294160A CN201811046888.7A CN201811046888A CN109294160A CN 109294160 A CN109294160 A CN 109294160A CN 201811046888 A CN201811046888 A CN 201811046888A CN 109294160 A CN109294160 A CN 109294160A
- Authority
- CN
- China
- Prior art keywords
- parts
- added
- polyformaldehyde
- mass ratio
- composite material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/04—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonamides, polyesteramides or polyimides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2206—Oxides; Hydroxides of metals of calcium, strontium or barium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of polyformaldehyde composite materials and preparation method thereof, belong to field of polymer composite material.The present invention improves the interface bond strength of glass fibre and basalt fibre and acetal resin using glass fibre and basalt fibre as raw material, improves the wearability of matrix, while ultraviolet light can be absorbed has certain help to the ageing-resistant performance of material；The present invention is first reacted with decanedioic acid, hexamethylene diamine forms polyamide salt, and polyester soft segment exists with the effect for improving polymer flexible toughness and plasticity, improves compatibility；The crystalline rate that ethylene-acrylic acid copolymer, calcium hydroxide, melamine resin accelerate polyformaldehyde material is added in the present invention, has preferable thermal stability, improves tensile strength and notch impact strength, improve the overall performance of polyformaldehyde composite material.The present invention solves current polyformaldehyde material and wears no resistance, poor mechanical property and the low problem of notch impact strength.
Description
Technical field
The invention belongs to field of polymer composite material, and in particular to a kind of polyformaldehyde composite material and preparation method thereof.
Background technique
Polyformaldehyde is one of five large-engineering plastics, has high-modulus, high rigidity, endurance, self-lubricating, wear-resistant, size
The feature in the majority such as stable, is widely used in household electrical appliances, mechanical part, resistance to especially suitable for mechanical drive gear, lubrication bearing, axle sleeve etc.
Component is ground, is the light-weighted important foundation material of equipment.But polyformaldehyde easily decomposes generate formaldehyde low molecule in process
Object causes mechanics of materials intensity to decline, and causes environmental pollution, and it is higher not to be suitable for load, especially medical treatment, food machinery
Equal fields.
In recent years, it does a lot of work to polyoxymethylene modified aspect in the industry, from disclosed, most of is based on reducing it
The decomposition of process improves its wearability.It is such as improved as anti-wear agent using a large amount of polytetrafluoroethylene (PTFE) of addition or graphite
Therefore wearability but brings new problem, that is, forms Immiscible Polymer Blends, polyformaldehyde mechanical property is made to decline to a great extent；It adopts in the industry
Use the organic low molecular compounds such as low molecule formaldehyde catching agent such as dicyandiamide as formaldehyde absorbent, assimilation effect is preferable, adopts
Its processing fluidity is improved as lubricant with low-molecular-weight organic compound such as fatty acid or polyethylene wax, effectively improves poly- first
The processing fluidity of aldehyde.It is volatile in process or using but due to using a large amount of low-molecular-weight organic compound
Easy to migrate in journey, in parts surface formation low molecule film, friction process, this low molecule film, which had both been influenced material by thermal decomposition, to be made
Pollution is generated to environment again with the service life；Meanwhile it will lead to material mechanical performance using a large amount of low molecular compound and declining to a great extent.
A kind of fiberglass reinforced polyformaldehyde composite material is disclosed at present, polyformaldehyde: 40 ~ 70%, glass: 10 ~ 30%, TPU:5 ~
20%, PTFE:3 ~ 10%, antioxidant 1076: 0.1 ~ 0.5%, lubricant TAF0.1 ~ 0.5% improves the lubrication of polyformaldehyde, but does not solve
Certainly glass dispersion with it is exposed, parts surface is coarse, lead to problems such as material have wear no resistance.Therefore it needs to develop a kind of high resistance to
Grind high-intensitive polyformaldehyde composite material.
Summary of the invention
The technical problems to be solved by the invention: wearing no resistance for current polyformaldehyde material, poor mechanical property and notch
The low problem of impact strength provides a kind of polyformaldehyde composite material and preparation method thereof.
In order to solve the above technical problems, the present invention is using technical solution as described below:
A kind of polyformaldehyde composite material, including polyformaldehyde, fiber additive, induction crystallization additive, flexibilizer additive, lubrication
Agent, antioxidant；
The preparation method of the fiber additive, includes the following steps:
S1. take basalt fibre 3 ~ 6:7 in mass ratio ~ 10 be added glass fibre mixing, obtain composite fibre, take composite fibre through etc.
Gas ions handle 160 ~ 180s, obtain pretreatment of fiber, take silane coupling agent 2 ~ 5:10 in mass ratio ~ 20 that deionized water stirring is added
Mixing, obtains mixture；
S2. take mixture 30 ~ 50:3 in mass ratio ~ 5:1 ~ 3 that nano barite powder, molybdenum disulfide is added, ultrasound must impregnate
Liquid takes maceration extract 20 ~ 30:8 in mass ratio ~ 10 that pretreatment of fiber is added, is stirred in 35 ~ 40 DEG C, filters, and takes suction filtration slag dry
It is dry to get fiber additive.
Silane coupling agent in the step S1 are as follows:
Take allyl polyethenoxy polyoxypropylene epoxy group ether 1 ~ 3:10 in mass ratio ~ 15 be added deionized water, in 300r/min,
50 ~ 60 DEG C are stirred, and add three second of γ-aminopropyl of allyl polyethenoxy polyoxypropylene epoxy group ether quality 50 ~ 55%
Oxysilane is warming up to 80 ~ 100 DEG C of 2 ~ 4h of heat preservation, is cooled to room temperature to get silane coupling agent.
It is described induction crystallization additive the preparation method comprises the following steps:
According to the mass fraction, 5 ~ 10 parts of ethylene-acrylic acid copolymers, 3 ~ 7 parts of calcium hydroxides, 20 ~ 30 parts of melamine resins are taken, in
180 ~ 200 DEG C, 55r/min mixing, extruding pelletization to get.
The flexibilizer additive the preparation method comprises the following steps:
(1) it takes decanedioic acid 10 ~ 15:30 in mass ratio ~ 50 that dehydrated alcohol is added, the hexamethylene diamine of decanedioic acid quality 60 ~ 70% is added,
It is stirred in 40 ~ 50 DEG C, is freeze-dried, obtains freeze-drying object, take freeze-drying object 15 ~ 20:3 in mass ratio ~ 7:80 ~ 100
Adipic acid, deionized water is added, is kept the temperature in 240 ~ 260 DEG C, vacuumizes 2 ~ 4h of holding, obtain mixture；
(2) it takes mixture that Polyethylene glycol-2000 is added by 15 ~ 20:3 of quality ~ 5, the positive fourth of metatitanic acid of mixture quality 2 ~ 5% is added
Ester is passed through nitrogen protection, is warming up to 250 ~ 260 DEG C and is stirred, be cooled to room temperature, extrusion granulation obtains cooled material, by mass parts
Number meter takes 20 ~ 40 parts of cooled materials, 0.2 ~ 0.7 part of cumyl peroxide, 2 ~ 5 parts of maleic anhydrides, 60 ~ 80 parts of acetone stirrings mixed
It closes, in 175 ~ 185 DEG C of melting extrusions, is granulated to get flexibilizer additive.
The lubricant are as follows: take polyethylene wax 2 ~ 5:1 in mass ratio ~ 3 be added stearic acid mixing to get.
The antioxidant are as follows: four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol esters in mass ratio 8
~ 10:3 ~ 5 be added N- phenyl-α-naphthylamine mixing to get.
A kind of preparation method of polyformaldehyde composite material, includes the following steps:
According to the mass fraction, 200 ~ 300 parts of polyformaldehyde, 20 ~ 40 parts of fiber additives, 40 ~ 50 parts of inductions crystallization additives, 60 are taken
~ 90 parts of flexibilizer additives, 8 ~ 15 parts of lubricants, 3 ~ 9 parts of antioxidant mixing, are warming up to 240 ~ 260 DEG C, screw speed is
160r/min, feeding are given as squeezing out under conditions of 8Hz through melt blending, are granulated, dry, in 245 ~ 265 DEG C of injection moldings, obtain
Polyformaldehyde composite material.
The present invention is compared with other methods, and advantageous effects are:
(1) present invention is plasma-treated using glass fibre and basalt fibre as raw material, and fiber surface occurs different degrees of
Etching trace, and introduce oxygen-containing polar functional group, two-way interaction improve glass fibre and basalt fibre with
The interface bond strength of acetal resin, by allyl polyethenoxy polyoxypropylene epoxy group ether and gamma-aminopropyl-triethoxy
Silane mixture prepares macromolecular coupling agent, it modifies composite fibre, alkoxy base is contained in macromolecular coupling agent one end
Group, one end are contained unsaturated double-bond, can be chemically reacted respectively with fiber, acetal resin in use, in addition,
Since strand is longer, macromolecular is generated in composite material interface and is tangled, interface bond strength, nano barite, two are improved
The addition of molybdenum sulfide increases greasy property, reduces friction, improves the wearability of matrix, while ultraviolet light can be absorbed to material
Ageing-resistant performance has certain help；
(2) present invention first react with decanedioic acid, hexamethylene diamine and forms polyamide salt, adds adipic acid sealing end, be added catalyst with
Polyethylene glycol carries out polyesterification reaction, obtains block type polymers, and there are the effect of strong intermolecular hydrogen bonding, Ke Yifu in molecule
Its high stability and environment-responsive in polyformaldehyde composite material based on strong hydrogen bonding is given, on the one hand the active hydrogen in its structure
Addition reaction occurs with formaldehyde and plays the effect of the formaldehyde absorbent of polyformaldehyde to absorb the free formaldehyde in environment, it is opposite
Molecular mass is larger, and volatility, migration are very low, will not occur to lose in high-temperature fusion process or be precipitated, protect
Higher thermostabilization efficiency has been held, it is grafted with maleic anhydride on the other hand, forms flexibilizer additive, structure is maintained and relatively advises
The block copolymer that whole polyamide hard section and polyester soft segment are alternately constituted, polyester soft segment is to improve polymer flexible toughness and plastic
Property, the polyamide hard segment domains under two kinds of Hybrids of glassy state and crystalline state improve the resistance to of copolymer as crosslinking points
Viscosity flow and fixed member chain prevent its sliding, play the role of toughening and improve mechanical property, anhydride group therein can be with
The hydroxyl of fiber surface reacts to form chemical bond coordination plasticizing, improves compatibility；
(3) crystalline rate that ethylene-acrylic acid copolymer, calcium hydroxide, melamine resin accelerate polyformaldehyde material is added in the present invention,
On the one hand the formaldehyde for absorbing release in melting process, reduces the release of free formaldehyde, forms the composite material of environment-friendly type, another
Aspect passes through calcium hydroxide neutralization of ethylene-acrylic copolymer formation from aggressiveness, so that polyformaldehyde spherocrystal becomes smaller, crystallization nucleation
Rate is accelerated, and has preferable thermal stability, improves tensile strength and notch impact strength, improve polyformaldehyde composite material
Overall performance.
Specific embodiment
Nano barite powder: granularity 40nm；Molybdenum disulfide: granularity 80nm.
Induce crystallization additive the preparation method comprises the following steps:
According to the mass fraction, 5 ~ 10 parts of ethylene-acrylic acid copolymers, 3 ~ 7 parts of calcium hydroxides, 20 ~ 30 parts of melamine resins are taken, in
180 ~ 200 DEG C, 55r/min, 8 ~ 12min of mixing, extruding pelletization to get.
Flexibilizer additive the preparation method comprises the following steps:
(1) it takes decanedioic acid 10 ~ 15:30 in mass ratio ~ 50 that dehydrated alcohol is added, the hexamethylene diamine of decanedioic acid quality 60 ~ 70% is added,
Be stirred 1 ~ 3h in 40 ~ 50 DEG C, be freeze-dried, obtain freeze-drying object, take freeze-drying object 15 ~ 20:3 in mass ratio ~ 7:80 ~
100 addition adipic acids, deionized water vacuumize 2 ~ 4h of holding, obtain mixture in 240 ~ 260 DEG C of 50 ~ 60min of heat preservation；
(2) it takes mixture that polyethylene glycol is added by 15 ~ 20:3 of quality ~ 5, the tetrabutyl titanate of mixture quality 2 ~ 5% is added, lead to
Enter nitrogen protection, is warming up to 250 ~ 260 DEG C and is stirred 1 ~ 3h, be cooled to room temperature, extrusion granulation obtains cooled material, by mass parts
Number meter, takes 20 ~ 40 parts of cooled materials, 0.2 ~ 0.7 part of cumyl peroxide, 2 ~ 5 parts of maleic anhydrides, 60 ~ 80 parts of acetone, and stirring is mixed
1 ~ 3h is closed, in 175 ~ 185 DEG C of melting extrusions, is granulated to get flexibilizer additive.
Fiber additive the preparation method comprises the following steps:
S1. take basalt fibre 3 ~ 6:7 in mass ratio ~ 10 be added glass fibre mixing, obtain composite fibre, take composite fibre in
Plasma-treated 160 ~ the 180s of 11kHz, 20kV, 70W, obtains pretreatment of fiber, takes allyl polyethenoxy polyoxypropylene ring
Deionized water is added in oxygen ether 1 ~ 3:10 in mass ratio ~ 15, is stirred 20 ~ 30min in 300r/min, 50 ~ 60 DEG C, adds
The gamma-aminopropyl-triethoxy-silane of allyl polyethenoxy polyoxypropylene epoxy group ether quality 50 ~ 55%, is warming up to 80 ~ 100
DEG C heat preservation 2 ~ 4h, be cooled to room temperature, obtain cooled material a；
S2. it takes cooled material a 2 ~ 5:10 in mass ratio ~ 20 that deionized water is added, is stirred 20 ~ 30min, obtains mixture, take mixed
It closes object 30 ~ 50:3 in mass ratio ~ 5:1 ~ 3 and nano barite powder, molybdenum disulfide is added, 20 ~ 30min of ultrasound obtains maceration extract, takes
Pretreatment of fiber is added in maceration extract 20 ~ 30:8 in mass ratio ~ 10, is stirred 1 ~ 3h in 35 ~ 40 DEG C, filters, and takes suction filtration slag dry
It is dry to get fiber additive.
Lubricant: take polyethylene wax 2 ~ 5:1 in mass ratio ~ 3 be added stearic acid mixing to get.
Antioxidant: four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 8 ~ 10:3 in mass ratio ~
5 be added N- phenyl-α-naphthylamines mixing to get.
A kind of preparation method of polyformaldehyde composite material, includes the following steps:
According to the mass fraction, 200 ~ 300 parts of polyformaldehyde, 40 ~ 50 parts of induction crystallization additives, 60 ~ 90 parts of flexibilizer additives, 20 are taken
~ 40 parts of fiber additives, 8 ~ 15 parts of lubricants, 3 ~ 9 parts of antioxidant mixing, are warming up to 240 ~ 260 DEG C, are in screw speed
160r/min, feeding are given as squeezing out under conditions of 8Hz through melt blending, are granulated, dry, in 245 ~ 265 DEG C of injection moldings, obtain
Polyformaldehyde composite material.
Nano barite powder: granularity 40nm；Molybdenum disulfide: granularity 80nm.
Induce crystallization additive the preparation method comprises the following steps:
According to the mass fraction, 5 parts of ethylene-acrylic acid copolymers, 3 parts of calcium hydroxides, 20 parts of melamine resins are taken, in 180 DEG C, 55r/
Min, mixing 8min, extruding pelletization to get.
Flexibilizer additive the preparation method comprises the following steps:
(1) it takes decanedioic acid 10:30 in mass ratio that dehydrated alcohol is added, the hexamethylene diamine of decanedioic acid quality 60% is added, stirred in 40 DEG C
1h is mixed, freeze-drying obtains freeze-drying object, and take freeze-drying object 15:3:80 in mass ratio that adipic acid, deionized water is added,
In 240 DEG C of heat preservation 50min, vacuumizes and keep 2h, obtain mixture；
(2) it takes mixture that polyethylene glycol is added by quality 15:3, the tetrabutyl titanate of mixture quality 2% is added, be passed through nitrogen guarantor
Shield, is warming up to 250 DEG C and is stirred 1h, be cooled to room temperature, extrusion granulation, obtain cooled material, according to the mass fraction, take 20 parts of coolings
Object, 0.2 part of cumyl peroxide, 2 parts of maleic anhydrides, 60 parts of acetone, are stirred 1h, in 175 DEG C of melting extrusions, are granulated,
Up to flexibilizer additive.
Fiber additive the preparation method comprises the following steps:
S1. take basalt fibre 3:7 in mass ratio be added glass fibre mixing, obtain composite fibre, take composite fibre in 11kHz,
The plasma-treated 160s of 20kV, 70W, obtains pretreatment of fiber, takes allyl polyethenoxy polyoxypropylene epoxy group ether by matter
Deionized water is added than 1:10 in amount, is stirred 20min in 300r/min, 50 DEG C, adds allyl polyethenoxy polyoxy third
The gamma-aminopropyl-triethoxy-silane of alkene epoxy group ether quality 50% is warming up to 80 DEG C of heat preservation 2h, is cooled to room temperature, obtains cooled material
a；
S2. it takes cooled material a 2:10 in mass ratio that deionized water is added, is stirred 20min, obtains mixture, take mixture by matter
Nano barite powder, molybdenum disulfide is added than 30:3:1 in amount, and ultrasonic 20min obtains maceration extract, takes maceration extract 20:8 in mass ratio
Pretreatment of fiber is added, is stirred 1h in 35 DEG C, filters, takes and takes out filter residue and drying to get fiber additive.
Lubricant: take polyethylene wax 2:1 in mass ratio be added stearic acid mixing to get.
Antioxidant: four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 8:3 in mass ratio are added
N- phenyl-α-naphthylamine mixing to get.
A kind of preparation method of polyformaldehyde composite material, includes the following steps:
According to the mass fraction, 200 parts of polyformaldehyde, 40 parts of induction crystallization additives, 60 parts of flexibilizer additives, 20 parts of fiber additions are taken
Agent, 8 parts of lubricants, 3 parts of antioxidant mixing, are warming up to 240 DEG C, in screw speed is 160r/min, feeding is given as 8Hz's
Under the conditions of squeezed out through melt blending, be granulated, it is dry, in 245 DEG C of injection moldings, obtain polyformaldehyde composite material.
Nano barite powder: granularity 40nm；Molybdenum disulfide: granularity 80nm.
Induce crystallization additive the preparation method comprises the following steps:
According to the mass fraction, 8 parts of ethylene-acrylic acid copolymers, 5 parts of calcium hydroxides, 25 parts of melamine resins are taken, in 190 DEG C, 55r/
Min, mixing 10min, extruding pelletization to get.
Flexibilizer additive the preparation method comprises the following steps:
(1) it takes decanedioic acid 13:40 in mass ratio that dehydrated alcohol is added, the hexamethylene diamine of decanedioic acid quality 65% is added, stirred in 45 DEG C
2h is mixed, freeze-drying obtains freeze-drying object, and take freeze-drying object 17:5:90 in mass ratio that adipic acid, deionized water is added,
In 250 DEG C of heat preservation 55min, vacuumizes and keep 3h, obtain mixture；
(2) it takes mixture that polyethylene glycol is added by quality 18:4, the tetrabutyl titanate of mixture quality 3% is added, be passed through nitrogen guarantor
Shield, is warming up to 255 DEG C and is stirred 2h, be cooled to room temperature, extrusion granulation, obtain cooled material, according to the mass fraction, take 30 parts of coolings
Object, 0.5 part of cumyl peroxide, 3 parts of maleic anhydrides, 70 parts of acetone, are stirred 2h, in 180 DEG C of melting extrusions, are granulated,
Up to flexibilizer additive.
Fiber additive the preparation method comprises the following steps:
S1. take basalt fibre 5:9 in mass ratio be added glass fibre mixing, obtain composite fibre, take composite fibre in 11kHz,
The plasma-treated 170s of 20kV, 70W, obtains pretreatment of fiber, takes allyl polyethenoxy polyoxypropylene epoxy group ether by matter
Deionized water is added than 2:13 in amount, is stirred 25min in 300r/min, 55 DEG C, adds allyl polyethenoxy polyoxy third
The gamma-aminopropyl-triethoxy-silane of alkene epoxy group ether quality 53% is warming up to 90 DEG C of heat preservation 3h, is cooled to room temperature, obtains cooled material
a；
S2. it takes cooled material a 3:15 in mass ratio that deionized water is added, is stirred 25min, obtains mixture, take mixture by matter
Nano barite powder, molybdenum disulfide is added than 40:4:2 in amount, and ultrasonic 25min obtains maceration extract, takes maceration extract 25:9 in mass ratio
Pretreatment of fiber is added, is stirred 2h in 37 DEG C, filters, takes and takes out filter residue and drying to get fiber additive.
Lubricant: take polyethylene wax 3:2 in mass ratio be added stearic acid mixing to get.
Antioxidant: four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 9:4 in mass ratio are added
N- phenyl-α-naphthylamine mixing to get.
A kind of preparation method of polyformaldehyde composite material, includes the following steps:
According to the mass fraction, 250 parts of polyformaldehyde, 45 parts of induction crystallization additives, 75 parts of flexibilizer additives, 30 parts of fiber additions are taken
Agent, 12 parts of lubricants, 6 parts of antioxidant mixing, are warming up to 250 DEG C, in screw speed is 160r/min, feeding is given as 8Hz
Under conditions of squeezed out through melt blending, be granulated, it is dry, in 255 DEG C of injection moldings, obtain polyformaldehyde composite material.
Nano barite powder: granularity 40nm；Molybdenum disulfide: granularity 80nm.
Induce crystallization additive the preparation method comprises the following steps:
According to the mass fraction, 10 parts of ethylene-acrylic acid copolymers, 7 parts of calcium hydroxides, 30 parts of melamine resins are taken, in 200 DEG C,
55r/min, mixing 12min, extruding pelletization to get.
Flexibilizer additive the preparation method comprises the following steps:
(1) it takes decanedioic acid 15:50 in mass ratio that dehydrated alcohol is added, the hexamethylene diamine of decanedioic acid quality 70% is added, stirred in 50 DEG C
3h is mixed, freeze-drying obtains freeze-drying object, and take freeze-drying object 20:7:100 in mass ratio that adipic acid, deionized water is added,
In 260 DEG C of heat preservation 60min, vacuumizes and keep 4h, obtain mixture；
(2) it takes mixture that polyethylene glycol is added by quality 20:5, the tetrabutyl titanate of mixture quality 5% is added, be passed through nitrogen guarantor
Shield, is warming up to 260 DEG C and is stirred 3h, be cooled to room temperature, extrusion granulation, obtain cooled material, according to the mass fraction, take 40 parts of coolings
Object, 0.7 part of cumyl peroxide, 5 parts of maleic anhydrides, 80 parts of acetone, are stirred 3h, in 185 DEG C of melting extrusions, are granulated,
Up to flexibilizer additive.
Fiber additive the preparation method comprises the following steps:
S1. take basalt fibre 6:10 in mass ratio be added glass fibre mixing, obtain composite fibre, take composite fibre in 11kHz,
The plasma-treated 180s of 20kV, 70W, obtains pretreatment of fiber, takes allyl polyethenoxy polyoxypropylene epoxy group ether by matter
Deionized water is added than 3:15 in amount, is stirred 30min in 300r/min, 60 DEG C, adds allyl polyethenoxy polyoxy third
The gamma-aminopropyl-triethoxy-silane of alkene epoxy group ether quality 55% is warming up to 100 DEG C of heat preservation 4h, is cooled to room temperature, obtains cooling
Object a；
S2. it takes cooled material a 5:20 in mass ratio that deionized water is added, is stirred 30min, obtains mixture, take mixture by matter
Nano barite powder, molybdenum disulfide is added than 50:5:3 in amount, and ultrasonic 30min obtains maceration extract, takes maceration extract in mass ratio 30:
10 are added pretreatment of fiber, are stirred 3h in 40 DEG C, filter, and take and take out filter residue and drying to get fiber additive.
Lubricant: take polyethylene wax 5:3 in mass ratio be added stearic acid mixing to get.
Antioxidant: four [β-(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 10:5 in mass ratio add
Enter N- phenyl-α-naphthylamine mixing to get.
A kind of preparation method of polyformaldehyde composite material, includes the following steps:
According to the mass fraction, 300 parts of polyformaldehyde, 50 parts of induction crystallization additives, 90 parts of flexibilizer additives, 40 parts of fiber additions are taken
Agent, 15 parts of lubricants, 9 parts of antioxidant mixing, are warming up to 260 DEG C, in screw speed is 160r/min, feeding is given as 8Hz
Under conditions of squeezed out through melt blending, be granulated, it is dry, in 265 DEG C of injection moldings, obtain polyformaldehyde composite material.
Comparative example 1: it is essentially identical with the preparation method of embodiment 1, it has only the difference is that lacking fiber additive.
Comparative example 2: it is essentially identical with the preparation method of embodiment 1, it has only the difference is that lacking lubricant.
Comparative example 3: it is essentially identical with the preparation method of embodiment 1, it has only the difference is that lacking flexibilizer additive.
Comparative example 4: it is essentially identical with the preparation method of embodiment 1, it has only the difference is that lacking antioxidant.
Comparative example 5: the polyformaldehyde composite material of Shanghai City company production.
By polyformaldehyde composite material obtained by embodiment and comparative example according to GB/T 9341-2008, GB/T 1040.2-
2006, GB/T 1843-2008 standard is tested, and test result is as shown in table 1.
Table 1:
| Test item | Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 |
| Tensile strength (MPa) | 190 | 186 | 189 | 165 | 162 | 161 | 171 | 109 |
| Bending strength (MPa) | 251 | 248 | 249 | 231 | 235 | 230 | 239 | 158 |
| Notch impact strength (kJ/m2) | 25.1 | 24.6 | 24.9 | 21.3 | 23.6 | 23.2 | 21.3 | 10.9 |
| It wears away (mg) | 6 | 9 | 7 | 10 | 13 | 12 | 14 | 45 |
| Friction Temperature Rise (DEG C) | 10 | 12 | 11 | 15 | 14 | 16 | 13 | 36 |
The foregoing is merely preferred modes of the invention, are not intended to limit the invention, it is all the spirit and principles in the present invention it
Interior, any modification, equivalent replacement, improvement and so on should all be included in the protection scope of the present invention.In conclusion this
The polyformaldehyde composite material of invention has high-intensitive super abrasive characteristic, more preferable compared to commercial product effect, is worth pushing greatly
Extensively.
Claims (7)
1. a kind of polyformaldehyde composite material, which is characterized in that including polyformaldehyde, fiber additive, induction crystallization additive, toughening
Additive, lubricant, antioxidant；
The preparation method of the fiber additive, includes the following steps:
S1. take basalt fibre 3 ~ 6:7 in mass ratio ~ 10 be added glass fibre mixing, obtain composite fibre, take composite fibre through etc.
Gas ions handle 160 ~ 180s, obtain pretreatment of fiber, take silane coupling agent 2 ~ 5:10 in mass ratio ~ 20 that deionized water stirring is added
Mixing, obtains mixture；
S2. take mixture 30 ~ 50:3 in mass ratio ~ 5:1 ~ 3 that nano barite powder, molybdenum disulfide is added, ultrasound must impregnate
Liquid takes maceration extract 20 ~ 30:8 in mass ratio ~ 10 that pretreatment of fiber is added, is stirred in 35 ~ 40 DEG C, filters, and takes suction filtration slag dry
It is dry to get fiber additive.
2. polyformaldehyde composite material according to claim 1, which is characterized in that the silane coupling agent in the step S1
Are as follows:
Take allyl polyethenoxy polyoxypropylene epoxy group ether 1 ~ 3:10 in mass ratio ~ 15 be added deionized water, in 300r/min,
50 ~ 60 DEG C are stirred, and add three second of γ-aminopropyl of allyl polyethenoxy polyoxypropylene epoxy group ether quality 50 ~ 55%
Oxysilane is warming up to 80 ~ 100 DEG C of 2 ~ 4h of heat preservation, is cooled to room temperature to get silane coupling agent.
3. polyformaldehyde composite material according to claim 1, which is characterized in that the preparation side of the induction crystallization additive
Method are as follows: according to the mass fraction, 5 ~ 10 parts of ethylene-acrylic acid copolymers, 3 ~ 7 parts of calcium hydroxides, 20 ~ 30 parts of melamine resins are taken, in
180 ~ 200 DEG C, 55r/min mixing, extruding pelletization to get.
4. polyformaldehyde composite material according to claim 1, which is characterized in that the preparation method of the flexibilizer additive
Are as follows:
(1) it takes decanedioic acid 10 ~ 15:30 in mass ratio ~ 50 that dehydrated alcohol is added, the hexamethylene diamine of decanedioic acid quality 60 ~ 70% is added,
It is stirred in 40 ~ 50 DEG C, is freeze-dried, obtains freeze-drying object, take freeze-drying object 15 ~ 20:3 in mass ratio ~ 7:80 ~ 100
Adipic acid, deionized water is added, is kept the temperature in 240 ~ 260 DEG C, vacuumizes 2 ~ 4h of holding, obtain mixture；
(2) it takes mixture that Polyethylene glycol-2000 is added by 15 ~ 20:3 of quality ~ 5, the positive fourth of metatitanic acid of mixture quality 2 ~ 5% is added
Ester is passed through nitrogen protection, is warming up to 250 ~ 260 DEG C and is stirred, be cooled to room temperature, extrusion granulation obtains cooled material, by mass parts
Number meter takes 20 ~ 40 parts of cooled materials, 0.2 ~ 0.7 part of cumyl peroxide, 2 ~ 5 parts of maleic anhydrides, 60 ~ 80 parts of acetone stirrings mixed
It closes, in 175 ~ 185 DEG C of melting extrusions, is granulated to get flexibilizer additive.
5. polyformaldehyde composite material according to claim 1, which is characterized in that the lubricant are as follows: take polyethylene wax by
2 ~ 5:1 of mass ratio ~ 3 be added stearic acid mixing to get.
6. polyformaldehyde composite material according to claim 1, which is characterized in that the antioxidant are as follows: four [β-(3,5-
Di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester 8 ~ 10:3 in mass ratio ~ 5 addition N- phenyl-α-naphthylamine mixing, i.e.,
?.
7. a kind of preparation method of the polyformaldehyde composite material as described in claim 1 ~ 6 any one, which is characterized in that the system
Preparation Method include the following steps: according to the mass fraction, take 200 ~ 300 parts of polyformaldehyde, 20 ~ 40 parts of fiber additives, 40 ~ 50 parts lure
Crystallization additive, 60 ~ 90 parts of flexibilizer additives, 8 ~ 15 parts of lubricants, 3 ~ 9 parts of antioxidant mixing are led, are warming up to 240 ~ 260
DEG C, screw speed 160r/min, feeding are given as squeezing out under conditions of 8Hz through melt blending, are granulated, and it is dry, in 245 ~ 265
DEG C injection molding, obtains polyformaldehyde composite material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811046888.7A CN109294160A (en) | 2018-09-08 | 2018-09-08 | A kind of polyformaldehyde composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811046888.7A CN109294160A (en) | 2018-09-08 | 2018-09-08 | A kind of polyformaldehyde composite material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109294160A true CN109294160A (en) | 2019-02-01 |
Family
ID=65166586
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811046888.7A Withdrawn CN109294160A (en) | 2018-09-08 | 2018-09-08 | A kind of polyformaldehyde composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109294160A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111548598A (en) * | 2020-06-17 | 2020-08-18 | 湖北合聚高分子材料有限公司 | Aging-resistant high-toughness polyformaldehyde material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5559180A (en) * | 1993-03-22 | 1996-09-24 | E. I. Du Pont De Nemours And Company | Polyacetal compositions for use in wear applications |
| CN102942764A (en) * | 2012-11-20 | 2013-02-27 | 开滦能源化工股份有限公司 | High-content fiber-reinforced polyoxymethylene composite material and preparation method thereof |
| CN103497482A (en) * | 2013-08-23 | 2014-01-08 | 开滦能源化工股份有限公司 | High-wear resistance reinforced polyformaldehyde composite material and preparation method thereof |
| CN105086341A (en) * | 2015-09-14 | 2015-11-25 | 苏州法斯特信息科技有限公司 | Flame retardant and toughened polyformaldehyde composite material and preparation method thereof |
-
2018
- 2018-09-08 CN CN201811046888.7A patent/CN109294160A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5559180A (en) * | 1993-03-22 | 1996-09-24 | E. I. Du Pont De Nemours And Company | Polyacetal compositions for use in wear applications |
| CN102942764A (en) * | 2012-11-20 | 2013-02-27 | 开滦能源化工股份有限公司 | High-content fiber-reinforced polyoxymethylene composite material and preparation method thereof |
| CN103497482A (en) * | 2013-08-23 | 2014-01-08 | 开滦能源化工股份有限公司 | High-wear resistance reinforced polyformaldehyde composite material and preparation method thereof |
| CN105086341A (en) * | 2015-09-14 | 2015-11-25 | 苏州法斯特信息科技有限公司 | Flame retardant and toughened polyformaldehyde composite material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 刘西文: "《塑料注射成型技术实用教程》", 31 October 2013, 印刷工业出版社 * |
| 唐磊 等: "《轻量化材料技术》", 31 January 2014, 国防工业出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111548598A (en) * | 2020-06-17 | 2020-08-18 | 湖北合聚高分子材料有限公司 | Aging-resistant high-toughness polyformaldehyde material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109957239B (en) | Thermoplastic reinforced bio-based PA56/PA66 alloy and preparation method thereof | |
| CN101864168B (en) | Wear-resistant self-lubricating nylon compound material and method for preparing same | |
| CN1216101C (en) | Preparation method of toughness enhanced and reinforced polybutanediol terephthalate nanometer composition | |
| CN104371162A (en) | Flame-retardant wear-resisting modified polypropylene material and preparation method thereof | |
| CN102391432B (en) | High-fluidity ethylene-alpha-octene graft copolymer and preparation method thereof | |
| CN108164820A (en) | A kind of plant fiber/PP composite materials and preparation method thereof | |
| CN101921485A (en) | Compound fiber reinforced antistatic polyphenylene sulfide composite material and preparation method thereof | |
| CN108530888A (en) | A kind of high-strength wearable PA66 composite material and preparation methods | |
| CN104004348A (en) | High-thermal-oxidative stability and heat-resistant regeneration nylon material and preparation method thereof | |
| CN102417690A (en) | Polyformaldehyde composite material and preparation method thereof | |
| CN105237943B (en) | A kind of rigidity reinforced polyformaldehyde composite material and preparation method thereof | |
| CN105754336A (en) | PA66 composite material composition with favorable appearance and high static pressure resistance and preparation method of PA66 composite material composition | |
| CN103497482A (en) | High-wear resistance reinforced polyformaldehyde composite material and preparation method thereof | |
| CN102585495A (en) | Hydrolysis-resistant glass fiber reinforced polyamide 66 (PA66) composite material and preparation method thereof | |
| CN111621148A (en) | High-wear-resistance bio-based PA56 composite material and preparation method thereof | |
| CN109294160A (en) | A kind of polyformaldehyde composite material and preparation method thereof | |
| CN110982262A (en) | Wear-resistant reinforced long-carbon-chain nylon PA1012 composite material and preparation method thereof | |
| CN111117224A (en) | Low-water-absorption glass fiber reinforced polyamide material and preparation method thereof | |
| CN111484731A (en) | High-modulus flame-retardant reinforced nylon composite material and preparation method thereof | |
| CN109957238B (en) | Thermoplastic flame-retardant bio-based PA56 and PA66 composite material and preparation method thereof | |
| CN103304994A (en) | Wearable and hydrolysis-resistant enhanced nylon 66 composite material | |
| CN105968801A (en) | High-performance modified polyamide composite material and preparation method thereof | |
| CN103571182A (en) | High-fluidity toughened filling nylon and preparation method thereof | |
| CN1847299A (en) | Ultrahigh molecular weight polyethylene composition capable of being extrusion molded and its prepn process | |
| CN106479051A (en) | A kind of anti-static and abrasion-resistant polypropylene poly styrene composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20190201 |