CN108102355A - A kind of high cold-resistant polyamide and preparation method thereof - Google Patents
A kind of high cold-resistant polyamide and preparation method thereof Download PDFInfo
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- CN108102355A CN108102355A CN201711475594.1A CN201711475594A CN108102355A CN 108102355 A CN108102355 A CN 108102355A CN 201711475594 A CN201711475594 A CN 201711475594A CN 108102355 A CN108102355 A CN 108102355A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- 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
- C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
- C08K2003/2213—Oxides; Hydroxides of metals of rare earth metal of cerium
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- 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
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Abstract
The invention discloses a kind of high cold-resistant polyamide, belong to resin making technique field, the height resists cold polyamide, including following raw material：Polyamide, silicon rubber, ethylene propylene diene rubber, chlorosulfonated polyethylene rubber, two fluororesin of segregation, styrene-acrylic emulsion, poly- fluorine ethylene resin, polyphosphate, sebacic acid dibutyl ester, trioctyl trimellitate (TOTM), dioctyl phthalate, carbon black master batch, clay, jade powder, zinc stearate, trbasic zinc phosphate, chlorinated paraffin, glass fibre, trioctyl trimellitate (TOTM), sebacic acid dibutyl ester, antimony oxide, cerium oxide, silane coupling agent KH 560, cold-resistant modified additive, the height polyamide that resists cold is by preparing base-material, prepare modified materials, and by base-material, the materials such as modified materials mixing and etc. made of.The polyamide that the present invention is prepared has excellent cold tolerance.
Description
Technical field
The present invention relates to the technical field of resin preparation process more particularly to a kind of high cold-resistant polyamide and its preparations
Method.
Background technology
Polyamide has preferable resistance to chemical reagents, can resist soda acid and vegetable oil, mineral oil etc..Chinese patent application
A kind of document " polyamide and preparation method thereof (application publication number：CN105885036A a kind of polyamide) " is disclosed
And preparation method thereof, main chain contains propane diamine unit and oxalic acid unit, wherein, propane diamine unit from 1,2- propane diamine,
The mixture of 1,3-PD or both, the preparation method of the polyamide, includes the following steps：In the presence of the solvent
Or it is solvent-free in the case of, the diamine monomer system containing propylene glycol and oxalate diester monomer are mixed, in room temperature to 150 DEG C of temperature
Degree is lower to carry out prepolymerization, obtains prepolymer, the prepolymer of gained is carried out melt polymerization or solid phase, obtains polyamide resin
Fat does not change polyamide high temperature resistant, low water suction, and monomer used is easy to get extensively, cheap.But its cold tolerance can not
The needs of meeting in actual use.
The content of the invention
To solve technical problem present in background technology, the present invention proposes a kind of high cold-resistant polyamide and its preparation
Method, to solve in a kind of Chinese patent application document " polyamide and preparation method thereof (application publication number：
CN105885036A the problem of polyamide cold tolerance is insufficient disclosed in) ".
A kind of high cold-resistant polyamide proposed by the present invention, including following raw material：Polyamide, silicon rubber, ternary
EP rubbers, chlorosulfonated polyethylene rubber, two fluororesin of segregation, styrene-acrylic emulsion, poly- fluorine ethylene resin, polyphosphate, sebacic acid
Dibutyl ester, trioctyl trimellitate (TOTM), dioctyl phthalate, carbon black master batch, clay, jade powder, zinc stearate, trbasic zinc phosphate,
Chlorinated paraffin, glass fibre, trioctyl trimellitate (TOTM), sebacic acid dibutyl ester, antimony oxide, cerium oxide, silane coupling agent KH-
560th, resist cold modified additive；
The antimony oxide, cerium oxide, silane coupling agent KH-560, the weight ratio of cold-resistant modified additive are (6-8)：
(12-16)：(1-3)：(20-40).
Further, the antimony oxide, cerium oxide, silane coupling agent KH-560, the weight ratio of cold-resistant modified additive
For 7：14：2：30.
Further, in units of parts by weight, including following raw material：80-120 parts of polyamide, silicon rubber 20-40
Part, 15-25 parts of ethylene propylene diene rubber, 5-15 parts of chlorosulfonated polyethylene rubber, 6-12 parts of two fluororesin of segregation, styrene-acrylic emulsion 4-8
Part, 3-9 parts of poly- fluorine ethylene resin, 2-6 parts of polyphosphate, 1-5 parts of sebacic acid dibutyl ester, 3-5 parts of trioctyl trimellitate (TOTM), adjacent benzene
2-6 parts of diformazan dioctyl phthalate, 3-6 parts of carbon black master batch, 4-8 parts of clay, 3-5 parts of jade powder, 1-5 parts of zinc stearate, trbasic zinc phosphate 3-5
Part, 2-4 parts of chlorinated paraffin, 3-5 parts of glass fibre, 1-5 parts of trioctyl trimellitate (TOTM), 3-6 parts of sebacic acid dibutyl ester, three oxidations two
6-8 parts of antimony, 12-16 parts of cerium oxide, 1-3 parts of silane coupling agent KH-560, cold-resistant 20-40 parts of modified additive.
Further, the raw material of the cold-resistant modified additive includes by weight：5-15 parts of diatomite, carbon nanotubes 4-8
Part, 4-8 parts of 3-9 parts of 10-20 parts of the concentrated sulfuric acid, allyl alcohol, the chloroplatinic acid that mass fraction is 85-95%.
Further, the cold-resistant modified additive is prepared by following technique：By diatomite, carbon nanotubes and quality point
Number is uniformly mixed for the concentrated sulfuric acid of 85-95%, is warming up to 80-90 DEG C, stirs 2-4h in 650-850r/min rotating speeds, is washed after filtering
It washs, filters, dry, grinding crosses 150-250 mesh sieves and obtains material a；Allyl alcohol is added in into material a to be uniformly mixed, and is warming up to
It 85-95 DEG C, then adds chloroplatinic acid and is uniformly mixed, be warming up to 95-105 DEG C, keep the temperature 1-3h, stirred in 650-850r/min rotating speeds
10-20min is cooled to room temperature to obtain cold-resistant modified additive.
The present invention also provides a kind of preparation methods of high cold-resistant polyamide, include the following steps：
S1, by polyamide, silicon rubber, ethylene propylene diene rubber, chlorosulfonated polyethylene rubber, two fluororesin of segregation, benzene
Acrylic emulsion, poly- fluorine ethylene resin are uniformly mixed, and are stirred 10-30min in 850-1050r/min rotating speeds, are warming up to 80-90 DEG C, protect
Then warm 20-40min adds in polyphosphate, sebacic acid dibutyl ester, trioctyl trimellitate (TOTM), dioctyl phthalate, carbon black
Master batch, clay, jade powder, zinc stearate, trbasic zinc phosphate, chlorinated paraffin, glass fibre, trioctyl trimellitate (TOTM), two fourth of sebacic acid
Ester is uniformly mixed, and ball milling postcooling to room temperature obtains base-material；
S2, antimony oxide, cerium oxide, cold-resistant modified additive are uniformly mixed, are warming up to 60-80 DEG C, keep the temperature 10-
Then 20min adds in silane coupling agent KH-560 and is uniformly mixed, is continuously heating to 110-120 DEG C, keeps the temperature 5-15min, be cooled to
Room temperature obtains modified materials；
S3, base-material is warming up to 90-110 DEG C, keeps the temperature 15-35min, be subsequently added into modified materials and be uniformly mixed, be cooled to 80-
90 DEG C, 20-30min is kept the temperature, then stirs 1-2h in 1350-1550r/min rotating speeds, is cooled to room temperature to obtain high cold-resistant polyamide
Resin.
The invention has the advantages that：
(1) by the data of embodiment 1-3 and comparative example 6 as it can be seen that using the cold-resistant of the cold-resistant polyamides of embodiment 1-3 high
Performance significantly improves；Simultaneously by the data of embodiment 1-3 as it can be seen that embodiment 1 is optimum embodiment.
(2) by embodiment 1 and the data of comparative example 1-5 as it can be seen that antimony oxide, cerium oxide, silane coupling agent KH-560,
Cold-resistant modified additive adds simultaneously plays synergistic effect in high cold-resistant polyamide is prepared, and significantly improves high cold-resistant poly-
The cold tolerance of amide resin, this may be：Antimony oxide, cerium oxide, silane coupling agent KH-560, cold-resistant modified additive are made
It is applied to for modified system in the preparation of polyamide, the graft modification of silane coupling agent KH-560 make use of to act on, realized
The base-material of antimony oxide, the hydroxyl of cerium oxide and cold-resistant modified additive surface and polyamide realizes grafting, imparts
The excellent cold tolerance of polyamide, while the cold-resistant humidification of cold-resistant modified additive is make use of, wherein cold-resistant modification helps
By the way that the concentrated sulfuric acid that diatomite, carbon nanotubes and mass fraction are 85% is uniformly mixed, heating, stirring is washed after filtering for agent,
It filters, dries, grinding, sieving obtains material a；Allyl alcohol is added in into material a to be uniformly mixed, and is heated up, is then added chlorine platinum
Acid is uniformly mixed, and is heated up, and is kept the temperature, stirring, is cooled to room temperature to obtain cold-resistant modified additive, is applied to polyamide of the present invention
In preparation, under the action of silane coupling agent KH-560, realize and carry out grafting with the major ingredient of polyamide and combined, effectively carry
The high cold tolerance of polyamide.
Specific embodiment
The present invention is described in detail with reference to specific embodiment, it should be appreciated that embodiment is served only for illustrating this hair
Bright rather than for limiting the invention, any modification made on the basis of the present invention, equivalent substitution etc. are in this hair
In bright protection domain.
In embodiment, the high cold-resistant polyamide, in units of parts by weight, including following raw material：Polyamide resin
80-120 parts of fat, 20-40 parts of silicon rubber, 15-25 parts of ethylene propylene diene rubber, 5-15 parts of chlorosulfonated polyethylene rubber, segregation difluoro
6-12 parts of resin, 4-8 parts of styrene-acrylic emulsion, 3-9 parts of poly- fluorine ethylene resin, 2-6 parts of polyphosphate, 1-5 parts of sebacic acid dibutyl ester, partially
3-5 parts of three monooctyl ester of benzenetricarboxylic acid, 2-6 parts of dioctyl phthalate, 3-6 parts of carbon black master batch, 4-8 parts of clay, 3-5 parts of jade powder,
1-5 parts of zinc stearate, 3-5 parts of trbasic zinc phosphate, 2-4 parts of chlorinated paraffin, 3-5 parts of glass fibre, 1-5 parts of trioctyl trimellitate (TOTM), certain herbaceous plants with big flowers
3-6 parts of adipate, 6-8 parts of antimony oxide, 12-16 parts of cerium oxide, 1-3 parts of silane coupling agent KH-560, cold-resistant modification
20-40 parts of auxiliary agent.
The cold-resistant modified additive is prepared by following technique：By weight by 5-15 parts of diatomite, 4-8 parts of nano-sized carbons
The concentrated sulfuric acid that pipe and 10-20 parts of mass fractions are 85-95% is uniformly mixed, and 80-90 DEG C is warming up to, in 650-850r/min rotating speeds
2-4h is stirred, is washed after filtering, is filtered, is dried, grinding crosses 150-250 mesh sieves and obtains material a；3-9 parts are added in into material a
Allyl alcohol is uniformly mixed, and is warming up to 85-95 DEG C, is then added 4-8 parts of chloroplatinic acids and is uniformly mixed, be warming up to 95-105 DEG C, protects
Warm 1-3h stirs 10-20min in 650-850r/min rotating speeds, is cooled to room temperature to obtain cold-resistant modified additive.
The preparation method of the high cold-resistant polyamide, comprises the following steps：
S1, by polyamide, silicon rubber, ethylene propylene diene rubber, chlorosulfonated polyethylene rubber, two fluororesin of segregation, benzene
Acrylic emulsion, poly- fluorine ethylene resin are uniformly mixed, and are stirred 10-30min in 850-1050r/min rotating speeds, are warming up to 80-90 DEG C, protect
Then warm 20-40min adds in polyphosphate, sebacic acid dibutyl ester, trioctyl trimellitate (TOTM), dioctyl phthalate, carbon black
Master batch, clay, jade powder, zinc stearate, trbasic zinc phosphate, chlorinated paraffin, glass fibre, trioctyl trimellitate (TOTM), two fourth of sebacic acid
Ester is uniformly mixed, and ball milling postcooling to room temperature obtains base-material；
S2, antimony oxide, cerium oxide, cold-resistant modified additive are uniformly mixed, are warming up to 60-80 DEG C, keep the temperature 10-
Then 20min adds in silane coupling agent KH-560 and is uniformly mixed, is continuously heating to 110-120 DEG C, keeps the temperature 5-15min, be cooled to
Room temperature obtains modified materials；
S3, base-material is warming up to 90-110 DEG C, keeps the temperature 15-35min, be subsequently added into modified materials and be uniformly mixed, be cooled to 80-
90 DEG C, 20-30min is kept the temperature, then stirs 1-2h in 1350-1550r/min rotating speeds, is cooled to room temperature to obtain high cold-resistant polyamide
Resin.
Below by more specific embodiment, the present invention will be described.
Embodiment 1
A kind of high cold-resistant polyamide, in units of parts by weight, including following raw material：100 parts of polyamide, silicon rubber
30 parts of glue, 20 parts of ethylene propylene diene rubber, 10 parts of chlorosulfonated polyethylene rubber, 9 parts of two fluororesin of segregation, 6 parts of styrene-acrylic emulsion, poly- fluorine
6 parts of the dilute resin of second, 4 parts of polyphosphate, 3 parts of sebacic acid dibutyl ester, 4 parts of trioctyl trimellitate (TOTM), dioctyl phthalate 4
Part, 4.5 parts of carbon black master batch, 6 parts of clay, 4 parts of jade powder, 3 parts of zinc stearate, 4 parts of trbasic zinc phosphate, 3 parts of chlorinated paraffin, glass fibre
4 parts, 3 parts of trioctyl trimellitate (TOTM), 4.5 parts of sebacic acid dibutyl ester, 7 parts of antimony oxide, 14 parts of cerium oxide, silane coupling agent
2 parts of KH-560, cold-resistant 30 parts of modified additive.
The cold-resistant modified additive is prepared by following technique：By weight by 10 parts of diatomite, 6 parts of carbon nanotubes and
The concentrated sulfuric acid that 15 parts of mass fractions are 90% is uniformly mixed, and is warming up to 85 DEG C, is stirred 3h in 750r/min rotating speeds, is washed after filtering
It washs, filters, dry, grinding crosses 200 mesh sieves and obtains material a；6 parts of allyl alcohols are added in into material a to be uniformly mixed, and are warming up to
It 90 DEG C, then adds 6 parts of chloroplatinic acids and is uniformly mixed, be warming up to 100 DEG C, keep the temperature 2h, 15min is stirred in 750r/min rotating speeds, it is cold
But cold-resistant modified additive is obtained to room temperature.
The preparation method of the high cold-resistant polyamide, comprises the following steps：
S1, by polyamide, silicon rubber, ethylene propylene diene rubber, chlorosulfonated polyethylene rubber, two fluororesin of segregation, benzene
Acrylic emulsion, poly- fluorine ethylene resin are uniformly mixed, and are stirred 20min in 950r/min rotating speeds, are warming up to 85 DEG C, keep the temperature 30min, then
Add in polyphosphate, sebacic acid dibutyl ester, trioctyl trimellitate (TOTM), dioctyl phthalate, carbon black master batch, clay, jade
Powder, zinc stearate, trbasic zinc phosphate, chlorinated paraffin, glass fibre, trioctyl trimellitate (TOTM), sebacic acid dibutyl ester are uniformly mixed, ball milling
Postcooling to room temperature obtains base-material；
S2, antimony oxide, cerium oxide, cold-resistant modified additive are uniformly mixed, are warming up to 70 DEG C, keep the temperature 15min, then
It adds in silane coupling agent KH-560 to be uniformly mixed, is continuously heating to 115 DEG C, keep the temperature 10min, be cooled to room temperature to obtain modified materials；
S3, base-material is warming up to 100 DEG C, keeps the temperature 25min, be subsequently added into modified materials and be uniformly mixed, be cooled to 85 DEG C, heat preservation
25min then stirs 1.5h in 1450r/min rotating speeds, is cooled to room temperature to obtain high cold-resistant polyamide.
Embodiment 2
A kind of high cold-resistant polyamide, in units of parts by weight, including following raw material：80 parts of polyamide, silicon rubber
40 parts of glue, 15 parts of ethylene propylene diene rubber, 15 parts of chlorosulfonated polyethylene rubber, 6 parts of two fluororesin of segregation, 8 parts of styrene-acrylic emulsion, poly- fluorine
3 parts of the dilute resin of second, 6 parts of polyphosphate, 1 part of sebacic acid dibutyl ester, 5 parts of trioctyl trimellitate (TOTM), dioctyl phthalate 2
Part, 6 parts of carbon black master batch, 4 parts of clay, 5 parts of jade powder, 1 part of zinc stearate, 5 parts of trbasic zinc phosphate, 2 parts of chlorinated paraffin, glass fibre 5
Part, 1 part of trioctyl trimellitate (TOTM), 6 parts of sebacic acid dibutyl ester, 6 parts of antimony oxide, 16 parts of cerium oxide, silane coupling agent KH-
560 1 parts, cold-resistant 40 parts of modified additive.
The cold-resistant modified additive is prepared by following technique：By weight by 5 parts of diatomite, 8 parts of carbon nanotubes and
The concentrated sulfuric acid that 10 parts of mass fractions are 95% is uniformly mixed, and is warming up to 80 DEG C, is stirred 2h in 850r/min rotating speeds, is washed after filtering
It washs, filters, dry, grinding crosses 250 mesh sieves and obtains material a；3 parts of allyl alcohols are added in into material a to be uniformly mixed, and are warming up to
It 95 DEG C, then adds 4 parts of chloroplatinic acids and is uniformly mixed, be warming up to 105 DEG C, keep the temperature 1h, 10min is stirred in 850r/min rotating speeds, it is cold
But cold-resistant modified additive is obtained to room temperature.
The preparation method of the high cold-resistant polyamide, comprises the following steps：
S1, by polyamide, silicon rubber, ethylene propylene diene rubber, chlorosulfonated polyethylene rubber, two fluororesin of segregation, benzene
Acrylic emulsion, poly- fluorine ethylene resin are uniformly mixed, and are stirred 30min in 850r/min rotating speeds, are warming up to 80 DEG C, keep the temperature 40min, then
Add in polyphosphate, sebacic acid dibutyl ester, trioctyl trimellitate (TOTM), dioctyl phthalate, carbon black master batch, clay, jade
Powder, zinc stearate, trbasic zinc phosphate, chlorinated paraffin, glass fibre, trioctyl trimellitate (TOTM), sebacic acid dibutyl ester are uniformly mixed, ball milling
Postcooling to room temperature obtains base-material；
S2, antimony oxide, cerium oxide, cold-resistant modified additive are uniformly mixed, are warming up to 60 DEG C, keep the temperature 20min, then
It adds in silane coupling agent KH-560 to be uniformly mixed, is continuously heating to 110 DEG C, keep the temperature 15min, be cooled to room temperature to obtain modified materials；
S3, base-material is warming up to 90 DEG C, keeps the temperature 35min, be subsequently added into modified materials and be uniformly mixed, be cooled to 80 DEG C, heat preservation
30min then stirs 2h in 1350r/min rotating speeds, is cooled to room temperature to obtain high cold-resistant polyamide.
Embodiment 3
A kind of high cold-resistant polyamide, in units of parts by weight, including following raw material：120 parts of polyamide, silicon rubber
20 parts of glue, 25 parts of ethylene propylene diene rubber, 5 parts of chlorosulfonated polyethylene rubber, 12 parts of two fluororesin of segregation, 4 parts of styrene-acrylic emulsion, poly- fluorine
9 parts of the dilute resin of second, 2 parts of polyphosphate, 5 parts of sebacic acid dibutyl ester, 3 parts of trioctyl trimellitate (TOTM), dioctyl phthalate 6
Part, 3 parts of carbon black master batch, 8 parts of clay, 3 parts of jade powder, 5 parts of zinc stearate, 3 parts of trbasic zinc phosphate, 4 parts of chlorinated paraffin, glass fibre 3
Part, 5 parts of trioctyl trimellitate (TOTM), 3 parts of sebacic acid dibutyl ester, 8 parts of antimony oxide, 12 parts of cerium oxide, silane coupling agent KH-
560 3 parts, cold-resistant 20 parts of modified additive.
The cold-resistant modified additive is prepared by following technique：By weight by 15 parts of diatomite, 4 parts of carbon nanotubes and
The concentrated sulfuric acid that 20 parts of mass fractions are 85% is uniformly mixed, and is warming up to 90 DEG C, is stirred 4h in 650r/min rotating speeds, is washed after filtering
It washs, filters, dry, grinding crosses 150 mesh sieves and obtains material a；9 parts of allyl alcohols are added in into material a to be uniformly mixed, and are warming up to
It 85 DEG C, then adds 8 parts of chloroplatinic acids and is uniformly mixed, be warming up to 95 DEG C, keep the temperature 3h, 20min, cooling are stirred in 650r/min rotating speeds
Cold-resistant modified additive is obtained to room temperature.
The preparation method of the high cold-resistant polyamide, comprises the following steps：
S1, by polyamide, silicon rubber, ethylene propylene diene rubber, chlorosulfonated polyethylene rubber, two fluororesin of segregation, benzene
Acrylic emulsion, poly- fluorine ethylene resin are uniformly mixed, and are stirred 10min in 1050r/min rotating speeds, are warming up to 90 DEG C, keep the temperature 20min, so
Polyphosphate, sebacic acid dibutyl ester, trioctyl trimellitate (TOTM), dioctyl phthalate, carbon black master batch, clay, jade are added in afterwards
Mountain flour, zinc stearate, trbasic zinc phosphate, chlorinated paraffin, glass fibre, trioctyl trimellitate (TOTM), sebacic acid dibutyl ester are uniformly mixed, ball
Mill postcooling to room temperature obtains base-material；
S2, antimony oxide, cerium oxide, cold-resistant modified additive are uniformly mixed, are warming up to 80 DEG C, keep the temperature 10min, then
It adds in silane coupling agent KH-560 to be uniformly mixed, is continuously heating to 120 DEG C, keep the temperature 5min, be cooled to room temperature to obtain modified materials；
S3, base-material is warming up to 110 DEG C, keeps the temperature 15min, be subsequently added into modified materials and be uniformly mixed, be cooled to 90 DEG C, heat preservation
20min then stirs 1h in 1550r/min rotating speeds, is cooled to room temperature to obtain high cold-resistant polyamide.
Comparative example 1
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that in the raw material of the high cold-resistant polyamide of preparation
Lack antimony oxide, cerium oxide, silane coupling agent KH-560, cold-resistant modified additive.
Comparative example 2
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that in the raw material of the high cold-resistant polyamide of preparation
Lack antimony oxide.
Comparative example 3
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that in the raw material of the high cold-resistant polyamide of preparation
Lack cerium oxide.
Comparative example 4
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that in the raw material of the high cold-resistant polyamide of preparation
Lack silane coupling agent KH-560.
Comparative example 5
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that in the raw material of the high cold-resistant polyamide of preparation
Lack cold-resistant modified additive.
Comparative example 6
Using a kind of Chinese patent application document " polyamide and preparation method thereof (application publication number：
CN105885036A) " technique of embodiment 1 prepares polyamide.
The polyamide for measuring embodiment 1-3 and comparative example 1-6 carries out indices detection, and obtained testing result is such as
Following table：
| Experimental project | Low temperature resistant (DEG C) |
| Embodiment 1 | -65 |
| Embodiment 2 | -68 |
| Embodiment 3 | -67 |
| Comparative example 1 | -8 |
| Comparative example 2 | -58 |
| Comparative example 3 | -59 |
| Comparative example 4 | -61 |
| Comparative example 5 | -57 |
| Comparative example 6 | -5 |
(1) by the data of embodiment 1-3 and comparative example 6 as it can be seen that using the cold-resistant of the cold-resistant polyamides of embodiment 1-3 high
Performance significantly improves；Simultaneously by the data of embodiment 1-3 as it can be seen that embodiment 1 is optimum embodiment.
(2) by embodiment 1 and the data of comparative example 1-5 as it can be seen that antimony oxide, cerium oxide, silane coupling agent KH-560,
Cold-resistant modified additive adds simultaneously plays synergistic effect in high cold-resistant polyamide is prepared, and significantly improves high cold-resistant poly-
The cold tolerance of amide resin, this may be：Antimony oxide, cerium oxide, silane coupling agent KH-560, cold-resistant modified additive are made
It is applied to for modified system in the preparation of polyamide, the graft modification of silane coupling agent KH-560 make use of to act on, realized
The base-material of antimony oxide, the hydroxyl of cerium oxide and cold-resistant modified additive surface and polyamide realizes grafting, imparts
The excellent cold tolerance of polyamide, while the cold-resistant humidification of cold-resistant modified additive is make use of, wherein cold-resistant modification helps
By the way that the concentrated sulfuric acid that diatomite, carbon nanotubes and mass fraction are 85% is uniformly mixed, heating, stirring is washed after filtering for agent,
It filters, dries, grinding, sieving obtains material a；Allyl alcohol is added in into material a to be uniformly mixed, and is heated up, is then added chlorine platinum
Acid is uniformly mixed, and is heated up, and is kept the temperature, stirring, is cooled to room temperature to obtain cold-resistant modified additive, is applied to polyamide of the present invention
In preparation, under the action of silane coupling agent KH-560, realize and carry out grafting with the major ingredient of polyamide and combined, effectively carry
The high cold tolerance of polyamide.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art in the technical scope disclosed by the present invention, technique according to the invention scheme and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (6)
1. a kind of high cold-resistant polyamide, which is characterized in that including following raw material：Polyamide, silicon rubber, EPDM
Rubber, chlorosulfonated polyethylene rubber, two fluororesin of segregation, styrene-acrylic emulsion, poly- fluorine ethylene resin, polyphosphate, two fourth of sebacic acid
Ester, trioctyl trimellitate (TOTM), dioctyl phthalate, carbon black master batch, clay, jade powder, zinc stearate, trbasic zinc phosphate, chlorination
Paraffin, glass fibre, trioctyl trimellitate (TOTM), sebacic acid dibutyl ester, antimony oxide, cerium oxide, silane coupling agent KH-560,
Cold-resistant modified additive；
The antimony oxide, cerium oxide, silane coupling agent KH-560, the weight ratio of cold-resistant modified additive are (6-8)：(12-
16)：(1-3)：(20-40).
2. high cold-resistant polyamide according to claim 1, which is characterized in that the antimony oxide, cerium oxide, silicon
Alkane coupling agent KH-560, the weight ratio of cold-resistant modified additive are 7：14：2：30.
3. high cold-resistant polyamide according to claim 1 or 2, which is characterized in that in units of parts by weight, including with
Lower raw material：80-120 parts of polyamide, 20-40 parts of silicon rubber, 15-25 parts of ethylene propylene diene rubber, chlorosulfonated polyethylene rubber
5-15 parts, 6-12 parts of two fluororesin of segregation, 4-8 parts of styrene-acrylic emulsion, 3-9 parts of poly- fluorine ethylene resin, 2-6 parts of polyphosphate, certain herbaceous plants with big flowers two
1-5 parts of dibutyl phthalate, 3-5 parts of trioctyl trimellitate (TOTM), 2-6 parts of dioctyl phthalate, 3-6 parts of carbon black master batch, clay 4-8
Part, 3-5 parts of jade powder, 1-5 parts of zinc stearate, 3-5 parts of trbasic zinc phosphate, 2-4 parts of chlorinated paraffin, 3-5 parts of glass fibre, trimellitic acid
Three 1-5 parts of monooctyl esters, 3-6 parts of sebacic acid dibutyl ester, 6-8 parts of antimony oxide, 12-16 parts of cerium oxide, silane coupling agent KH-560
1-3 parts, cold-resistant 20-40 parts of modified additive.
4. according to the high cold-resistant polyamide of claim 1-3 any one of them, which is characterized in that the cold-resistant modified additive
Raw material include by weight：5-15 parts of diatomite, 4-8 parts of carbon nanotubes, the concentrated sulfuric acid 10-20 that mass fraction is 85-95%
Part, 3-9 parts of allyl alcohol, 4-8 parts of chloroplatinic acid.
5. according to the high cold-resistant polyamide of claim 1-4 any one of them, which is characterized in that the cold-resistant modified additive
It is prepared by following technique：The concentrated sulfuric acid that diatomite, carbon nanotubes and mass fraction are 85-95% is uniformly mixed, is heated up
To 80-90 DEG C, 2-4h is stirred in 650-850r/min rotating speeds, is washed after filtering, is filtered, is dried, 150-250 mesh sieves are crossed in grinding
Obtain material a；Allyl alcohol is added in into material a to be uniformly mixed, is warming up to 85-95 DEG C, is then added chloroplatinic acid and is uniformly mixed,
95-105 DEG C is warming up to, keeps the temperature 1-3h, 10-20min is stirred in 650-850r/min rotating speeds, is cooled to room temperature to obtain cold-resistant modification
Auxiliary agent.
A kind of 6. preparation method according to the high cold-resistant polyamide of claim 1-5 any one of them, which is characterized in that bag
Include following steps：
S1, by polyamide, silicon rubber, ethylene propylene diene rubber, chlorosulfonated polyethylene rubber, two fluororesin of segregation, phenylpropyl alcohol breast
Liquid, poly- fluorine ethylene resin are uniformly mixed, and are stirred 10-30min in 850-1050r/min rotating speeds, are warming up to 80-90 DEG C, keep the temperature 20-
40min, then add in polyphosphate, sebacic acid dibutyl ester, trioctyl trimellitate (TOTM), dioctyl phthalate, carbon black master batch,
Clay, jade powder, zinc stearate, trbasic zinc phosphate, chlorinated paraffin, glass fibre, trioctyl trimellitate (TOTM), the mixing of sebacic acid dibutyl ester
Uniformly, ball milling postcooling to room temperature obtains base-material；
S2, antimony oxide, cerium oxide, cold-resistant modified additive are uniformly mixed, are warming up to 60-80 DEG C, keep the temperature 10-20min, so
Silane coupling agent KH-560 is added in afterwards to be uniformly mixed, and is continuously heating to 110-120 DEG C, is kept the temperature 5-15min, be cooled to room temperature to obtain
Modified materials；
S3, base-material is warming up to 90-110 DEG C, keeps the temperature 15-35min, be subsequently added into modified materials and be uniformly mixed, be cooled to 80-90
DEG C, 20-30min is kept the temperature, then stirs 1-2h in 1350-1550r/min rotating speeds, is cooled to room temperature to obtain high cold-resistant polyamide resin
Fat.
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| CN106700562A (en) * | 2016-12-16 | 2017-05-24 | 安徽亚兰密封件有限公司 | High-hardness wear-resistant rubber sealing piece and preparation method thereof |
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| CN106750923A (en) * | 2016-12-12 | 2017-05-31 | 天长市康宁塑胶科技有限公司 | A kind of Flame-Retardant and Oil-Resistant modified plastic rubber material |
| CN106700562A (en) * | 2016-12-16 | 2017-05-24 | 安徽亚兰密封件有限公司 | High-hardness wear-resistant rubber sealing piece and preparation method thereof |
| CN107383451A (en) * | 2017-08-31 | 2017-11-24 | 安徽华海特种电缆集团有限公司 | The mobile grease proofing cold-resistant voltage-resistant flat electric cable material of one kind |
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