CN106893318A - Ultra-fine fully vulcanized powder rubber toughness reinforcing high-temperature-resnylont nylont material and preparation method thereof - Google Patents
Ultra-fine fully vulcanized powder rubber toughness reinforcing high-temperature-resnylont nylont material and preparation method thereof Download PDFInfo
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Abstract
The invention provides a kind of ultra-fine fully vulcanized powder rubber toughness reinforcing high-temperature-resnylont nylont material and preparation method thereof, the nylon material contains:25-75 parts of high temperature resistant nylon resin, 10-50 parts of plasticizing mother particle, 0-35 parts of reinforcer and 0.51-1.95 parts of auxiliary agent, plasticizing mother particle include that weight ratio is 1:1 dry high temperature resistant nylon resin and ultra-fine fully vulcanized powder rubber;The preparation method of nylon material includes:Plasticizing mother particle is first prepared, after then each raw material is mixed according to proportioning, ultra-fine fully vulcanized powder rubber toughness reinforcing high temperature resistant nylon composite material is obtained after extruded, check rod and pelletizing;The particle diameter of ultra-fine fully vulcanized powder rubber particle is smaller, surface area is larger, after high temperature resistant nylon resin is added into, easily form " pseudo-crystalline lattice " distributed architecture, can be dispersed in high temperature resistant nylon resin, the toughness of the composite being finally made can not only be increased substantially, moreover it is possible to composite is kept tensile strength and heat resisting temperature higher.
Description
Technical field
The invention belongs to high temperature resistant nylon composite material technical field, it is related to a kind of toughness reinforcing high temperature resistant nylon composite material and its preparation
Method.
Background technology
At present, with the development of industrial technology, the requirement such as auto industry can significantly reduce again while engine efficiency is improved
The discharge capacity of automobile fuel consumption and reduction vehicle exhaust, resistance to elevated temperatures requirement of the surface mounting technology to material is more next in electron trade
It is higher.
In order to solve problems, it is desirable to which material is provided simultaneously with the property such as lightweight, high temperature resistant, high intensity, dimensionally stable, fire-retardant
Can, therefore, high temperature resistant nylon turns into one of comparatively ideal material.Because high temperature resistant nylon can be some parts brings higher resistance to
Warm nature energy, or it is clear-cut metal material is instead of produce these parts, and also some fillers can be added strengthen other property
Can, so the development of high temperature resistant nylon makes it possible various products in terms of miniaturization, lightweight and powerful is realized.
But, the property of other fillers of the property for improving high temperature resistant nylon may be variant with the property of high temperature resistant nylon, causes
These fillers cannot be well dispersed in high temperature resistant nylon, so that preferable light weight effect is not only unable to reach, but also can
The mechanical performance (such as toughness) of high temperature resistant nylon can be influenceed, and then has influence on the industrial applications of high temperature resistant nylon.
The content of the invention
It is multiple it is an object of the invention to provide a kind of ultra-fine fully vulcanized powder rubber toughness reinforcing high temperature resistant nylon in order to solve the above problems
Condensation material, it not only has toughness higher, additionally it is possible to make tensile strength, mould of the high temperature resistant nylon resin matrix after being modified
Amount and heat distortion temperature will not occur significantly to reduce.
It is another object of the present invention to provide a kind of preparation of ultra-fine fully vulcanized powder rubber toughness reinforcing high temperature resistant nylon composite material
Method.
To reach above-mentioned purpose, solution of the invention is:
A kind of ultra-fine fully vulcanized powder rubber toughness reinforcing high temperature resistant nylon composite material, its weight for including following components and each component
Part is as follows:
Wherein, above-mentioned high temperature resistant nylon resin can be selected from PA46, PA9T, PA10T, the PA6T of fusing point between 285-315 DEG C
With any one or a few in polyphthalamide.
Above-mentioned plasticizing mother particle contains high temperature resistant nylon resin and ultra-fine fully vulcanized powder rubber.
Contain in the high temperature resistant nylon resin contained in plasticizing mother particle and ultra-fine fully vulcanized powder rubber toughness reinforcing high temperature resistant nylon composite material
The species of some high temperature resistant nylon resins can be with identical, but it is also possible to different.
Ultra-fine fully vulcanized powder rubber can be ultra-fine full vulcanization butadiene-styrene rubber, ultra-fine full vulcanization carboxylic styrene-butadiene rubber, ultra-fine full sulphur
In change ACM, ultra-fine full-sulfurized nitrile rubber, ultra-fine full vulcanization XNBR and ultra-fine full sulphurated siliastic
One or more.
The average grain diameter of ultra-fine full vulcanization butadiene-styrene rubber can be 100nm;And/or, it is ultra-fine it is full vulcanization carboxylic styrene-butadiene rubber it is average
Particle diameter can be 150nm;And/or, the average grain diameter of ultra-fine full vulcanized acrylate rubber can be 150nm;And/or, surpass
The average grain diameter of thin full-sulfurized nitrile rubber can be 100nm;And/or, the average grain diameter of ultra-fine full vulcanization XNBR can
Think 50nm;And/or, the average grain diameter of ultra-fine full sulphurated siliastic can be 100nm.
The weight ratio of high temperature resistant nylon resin and ultra-fine fully vulcanized powder rubber in plasticizing mother particle can be 1:1.
Reinforcer can be fine selected from talcum powder, wollastonite, sepiolite, calcium carbonate, mica powder, glass microballoon and milled glass
One or more in dimension.
Auxiliary agent can be selected from silane coupler, antioxidant, lubricant and nucleator in any one or a few.
Silane coupler can be N- β (aminoethyl)-γ-aminopropyltrimethoxysilane;Antioxidant can be N, N'- couples-(3- (3,5-
Di-tert-butyl-hydroxy phenyl) propiono) hexamethylene diamine and three (2.4- di-tert-butyl-phenyls) phosphite esters compounding;Lubricant
Can be any one in pentaerythritol stearate, calcium stearate or lithium stearate;Nucleator can be selected from Long carbon chain carboxylic acid
Calcium salt CVA102.
The weight portion of silane coupler can be 0-0.6 parts, when the weight portion of reinforcer is 0, the weight portion of silane coupler
Also it is 0;The weight portion of antioxidant can be 0.3-0.6 parts;The weight portion of lubricant can be 0.2-0.7 parts;The weight of nucleator
Amount part can be 0.01-0.05 parts.
A kind of method for preparing ultra-fine fully vulcanized powder rubber toughness reinforcing high temperature resistant nylon composite material described above, it includes following step
Suddenly:
(1), by the dried high temperature resistant nylon resin of 25-75 weight portions, the dried plasticizing mother particle of 10-50 weight portions, 0-35
The reinforcer of weight portion and the auxiliary agent mixing of 0.51-1.95 weight portions, obtain compound;
(2), by compound is extruded, check rod and pelletizing, obtain ultra-fine fully vulcanized powder rubber toughness reinforcing high temperature resistant nylon composite wood
Material.
Wherein, in step (1), plasticizing mother particle needs are previously prepared, and its preparation method comprises the following steps:Will be dried
High temperature resistant nylon resin and dried ultra-fine fully vulcanized powder rubber are 1 according to weight ratio:1 ratio is mixed, and is melted
Melt blending and extruding pelletization, obtain plasticizing mother particle.
The time of the mixing in step (1) can be 5 ± 5min.
Extrusion in step (2) is carried out in double screw extruder, extrusion temperature be 275-325 DEG C, double screw extruder feed
Material frequency is 10Hz, and main-machine screw rotating speed is 300r/min.
Due to using such scheme, the beneficial effects of the invention are as follows:
First, ultra-fine fully vulcanized powder rubber toughness reinforcing high temperature resistant nylon composite material of the invention contains high temperature resistant nylon resin and surpasses
Thin fully vulcanized powder rubber, because the degree of cross linking of the ultra-fine fully vulcanized powder rubber particle surface degree of cross linking higher, internal is relatively low,
Particle diameter is smaller and surface area is larger, so after ultra-fine fully vulcanized powder rubber particle is added into high temperature resistant nylon resin matrix, should
Ultra-fine fully vulcanized powder rubber particle easily forms " pseudo-crystalline lattice " distributed architecture, can be uniform in high temperature resistant nylon resin matrix
Dispersion, can not only increase substantially the toughness of the composite being finally made, additionally it is possible to the drawing for making the holding of composite higher
Stretch intensity and heat resisting temperature.
In addition, ultra-fine fully vulcanized powder rubber particle diameter is smaller and surface area is larger, it is difficult to be uniformly dispersed in resin matrix,
If being directly blended with high temperature resistant nylon plastic pellet, portion is easily floated thereon, cause mixing or blanking uneven so that screw rod
It is low when high during ultra-fine fully vulcanized powder rubber particle content in the screw rod of extruder, cause product unstable;If first with high temperature resistant
Nylon resin and ultra-fine fully vulcanized powder rubber are prepared into plasticizing mother particle, then again by plasticizing mother particle and high temperature resistant nylon resin alloy,
Equivalent to the time that increased fully vulcanized powder rubber particle and sheared in screw rod blending, contribute to ultra-fine fully vulcanized powder rubber grain
Son is uniformly dispersed in resin matrix.
Specific embodiment
The invention provides a kind of ultra-fine fully vulcanized powder rubber toughness reinforcing high temperature resistant nylon composite material and preparation method thereof.
<Ultra-fine fully vulcanized powder rubber toughness reinforcing high temperature resistant nylon composite material>
Weight portion of the ultra-fine fully vulcanized powder rubber toughness reinforcing high temperature resistant nylon composite material comprising following components and each component is as follows:
[high temperature resistant nylon resin]
High temperature resistant nylon resin can be any one in PA46, PA9T, PA10T, PA6T and polyphthalamide (PPA)
Plant or several.The fusing point of PA46, PA9T, PA10T, PA6T and polyphthalamide is between 285-315 DEG C.
[plasticizing mother particle]
Plasticizing mother particle contains high temperature resistant nylon resin and ultra-fine fully vulcanized powder rubber., it is necessary to fully dry before plasticizing mother particle is prepared
Dry high temperature resistant nylon resin and ultra-fine fully vulcanized powder rubber, can be by high temperature resistant nylon resin and ultra-fine fully vulcanized powder rubber point
4h is not dried in 110 DEG C of electric drying oven with forced convection, to obtain dry high temperature resistant nylon resin and dry ultra-fine full vulcanization
Powdered rubber.In the plasticizing mother particle being made, dried high temperature resistant nylon resin and dried ultra-fine fully vulcanized powder rubber
Weight ratio be 1:1.
Plasticizing mother particle can be prepared using following steps:
(1) high temperature resistant nylon resin and ultra-fine fully vulcanized powder rubber are fully dried;
(2) by dried high temperature resistant nylon resin and dried ultra-fine fully vulcanized powder rubber with 1:1 weight ratio is mixed
Close uniform, through double screw extruder melt blending and extruding pelletization, obtain plasticizing mother particle.
Wherein, in step (2), the extrusion temperature of double screw extruder is 275-325 DEG C, and main-machine screw rotating speed is 300r/min,
Feeding frequency is 10Hz.
The ultra-fine fully vulcanized powder rubber contained in plasticizing mother particle can (average grain diameter be selected from ultra-fine full vulcanization butadiene-styrene rubber
100nm), ultra-fine full vulcanization carboxylic styrene-butadiene rubber (average grain diameter is 150nm), ultra-fine full vulcanized acrylate rubber are (average
Particle diameter is 150nm), ultra-fine full-sulfurized nitrile rubber (average grain diameter is 100nm), ultra-fine full vulcanization XNBR it is (flat
Equal particle diameter is 50nm) and ultra-fine full sulphurated siliastic (average grain diameter is 100nm) in one or more.
The ultra-fine fully vulcanized powder rubber that the present invention is used is that one kind has cross-linked structure, particle diameter in nano level powdered rubber, is had
Not in traditional powdered rubber.Inventor has found under study for action:If by the addition of ultra-fine fully vulcanized powder rubber particle of the invention
When in high temperature resistant nylon resin matrix, because the degree of cross linking of ultra-fine fully vulcanized powder rubber particle surface is higher, case hardness is larger,
Thus have independent dispersiveness, between different ultra-fine fully vulcanized powder rubber particles will not adhesion, by the side for preparing master batch
Method crosses screw rod twice, increases the time of rubber particles shearing blending such that it is able to be evenly dispersed in high temperature resistant nylon of the invention
In resin matrix.In addition, inventor also found:The inside of ultra-fine fully vulcanized powder rubber particle has the relatively low degree of cross linking, still
So there is elasticity.Again because the particle diameter of ultra-fine fully vulcanized powder rubber particle is small, surface area is big, easily forms " pseudo-crystalline lattice " distribution
Structure, therefore, when the addition of ultra-fine fully vulcanized powder rubber particle is in high temperature resistant nylon resin matrix of the invention, not only may be used
To increase substantially the toughness of resin matrix, final obtained composite can be also simultaneously set to keep modulus and thermal deformation temperature higher
Degree.
[reinforcer]
Reinforcer can be fine selected from talcum powder, wollastonite, sepiolite, calcium carbonate, mica powder, glass microballoon and milled glass
One or more in dimension.However, according to actual conditions, can also be without reinforcer in material system of the invention.
[auxiliary agent]
Auxiliary agent can be selected from silane coupler, antioxidant, lubricant and nucleator in any one or a few.
Silane coupler can be N- β (aminoethyl)-γ-aminopropyltrimethoxysilane (SG-Si900), and the weight portion of addition can be with
It is 0-0.6 parts.When in the material system of the application without reinforcer, without addition silane coupler.
Antioxidant can be N, N'- couples-(3- (3,5- di-tert-butyl-hydroxy phenyls) propiono) hexamethylene diamine (antioxidant 1098)
With the compounding of three (2.4- di-tert-butyl-phenyls) phosphite ester (irgasfos 168s), the total addition weight portion of antioxidant can be 0.3-0.6
Part.
Lubricant can be any one in pentaerythritol stearate, calcium stearate and lithium stearate, and the weight portion of addition can
Think 0.2-0.7 parts.
Nucleator can be Long carbon chain carboxylic acid calcium salt CVA102, and the weight portion of addition can be 0.01-0.05 parts.
<The preparation method of ultra-fine fully vulcanized powder rubber toughness reinforcing high temperature resistant nylon composite material>
The preparation method of ultra-fine fully vulcanized powder rubber toughness reinforcing high temperature resistant nylon composite material comprises the following steps:
(1) plasticizing mother particle, is prepared;
(2) high temperature resistant nylon resin and plasticizing mother particle, are dried into 4 ± 2h in 110 ± 10 DEG C of electric drying oven with forced convection respectively;
(3), by the dried high temperature resistant nylon resin of 25-75 weight portions, the dried plasticizing mother particle of 10-50 weight portions, 0-35
The reinforcer of weight portion and the auxiliary agent of 0.51-1.95 weight portions mix 5 ± 5min in high-speed mixer, obtain compound;
(4), step (3) gained compound is placed in the main feeding hopper of double screw extruder, extruded by double screw extruder,
Check rod and pelletizing, obtain ultra-fine fully vulcanized powder rubber toughness reinforcing high temperature resistant nylon composite material.
Wherein, in step (4), the extrusion temperature of double screw extruder is 275-325 DEG C, and main-machine screw rotating speed is 300r/min,
Feeding frequency is 10Hz.
<Embodiment>
Below in conjunction with specific embodiment and comparative example, the present invention is further illustrated.
Embodiment 1 to 11
The preparation method of the ultra-fine fully vulcanized powder rubber toughness reinforcing high temperature resistant nylon composite material of embodiment 1 to 11 includes following step
Suddenly:
(1) a certain amount of high temperature resistant nylon resin and plasticizing mother particle, are dried into 4h in 110 DEG C of electric drying oven with forced convection respectively;
(2) high temperature resistant nylon resin that, will have been dried in step (1) according to the ratio of table 1 below or table 2 below, plasticizing mother particle and
Reinforcer, auxiliary agent are placed in and mix 5min in high-speed mixer, obtain compound;
(3), gained compound in step (2) is placed in the main feeding hopper of double screw extruder, is squeezed by double screw extruder
Go out, check rod and pelletizing, obtain ultra-fine fully vulcanized powder rubber toughness reinforcing high temperature resistant nylon composite material, the temperature of double screw extruder
It it is 275-325 DEG C, feeding frequency is 10HZ, main-machine screw rotating speed is 300r/min.
Wherein, in step (2), the preparation method of plasticizing mother particle is:Fully dried high temperature resistant nylon resin is complete with ultra-fine
Sulfide powder rubber is 1 according to weight ratio:1 ratio is placed at after high-speed mixer and mixing 5min by double screw extruder
Melt blending extruding pelletization, is obtained plasticizing mother particle.The temperature of double screw extruder is 275-325 DEG C, and feeding frequency is 10Hz,
Main-machine screw rotating speed is 300r/min.
In the preparation method of plasticizing mother particle, fully dried high temperature resistant nylon resin and fully dried ultra-fine full vulcanization powder
The weight portion of last rubber is 1:1, its reason is as follows:If the too high levels of ultra-fine fully vulcanized powder rubber in plasticizing mother particle,
The mobility for preparing system during plasticizing mother particle is poor, easy broken strip, it is difficult to smoothly production;Conversely, if content is too low,
More high temperature resistant nylon resin is accomplished by by extruder twice, production cost is high, and process is likely to result in product
Thermal decomposition, causes properties of product to be deteriorated.
The formula and procession parameters of the embodiment 1 to 5 of table 1
The formula and procession parameters of the embodiment 6 to 11 of table 2
The preparation method of the high temperature resistant nylon composite material of comparative example 1 to 5 comprises the following steps:
Be placed in for fully dried high temperature resistant nylon resin, toughener, reinforcer and auxiliary agent mixed at a high speed by the ratio according to table 3
Mix 5min in conjunction machine, then by double screw extruder melt blending extruding pelletization, obtain high temperature resistant composite.Wherein, it is double
The extrusion temperature of screw extruder is 275-325 DEG C, and feeding frequency is 10Hz, and main-machine screw rotating speed is 300r/min.
Wherein, toughener is in MBS-g-MAH, SEBS-g-MAH, EVA-g-GMA, EPDM-g-MAH and POE-g-MAH
Any one or a few, grafting rate is 1%.
The formula and procession parameters of the comparative example 1 to 5 of table 3
The present invention carries out performance characterization using following assay method:
1st, tensile strength:Tested according to ASTM D638-10;
2nd, bending modulus:Tested according to ASTM D790-10;
3rd, Izod notched impact strength:Tested according to ASTM D256-10;
4th, heat distortion temperature:Tested according to ASTM D648-07.
The test performance parameter of the composite of embodiment 1 to 4 and comparative example 1 to 4 is as shown in table 4 below.
The test performance table of the composite of the embodiment 1 to 4 of table 4 and comparative example 1 to 4
From the test data of table 3:
(1), more than the composite of comparative example 1 to 5, this explanation is in fact for the notch impact strength of the composite of embodiment 1 to 5
The composite of the toughness more than comparative example 1 to 5 of the composite of example 1 to 5 is applied, points out ultra-fine fully vulcanized powder rubber to have
Obvious toughening effect, because the particle diameter of ultra-fine fully vulcanized powder rubber particle is small, surface area is big, the energy in nylon matrix
Enough preferably dispersions, easily form " pseudo-crystalline lattice " distributed architecture, so toughening effect is substantially, and again can be compared with while toughness reinforcing
Make composite holding tensile strength higher, modulus and heat distortion temperature well.
(2) can be seen that the comprehensive comparison of the composite of embodiment 2 is good by the performance of upper table 3, be most preferred embodiment,
Tensile strength, bending modulus, the cantilever beam breach of prepared ultra-fine fully vulcanized powder rubber toughness reinforcing high temperature resistant nylon composite material
Impact strength highest, although heat distortion temperature is less than embodiment 3 and embodiment 4, and this is mainly by high temperature resistant nylon resin matrix
The influence (the high temperature resistant nylon resin matrix species of embodiment 2 is different with embodiment 3 and embodiment 4) of species.
(3) toughener used by the composite of comparative example 1-6 is MAH grafted elastomerics, and grafting rate is 1%, but due to
The equal non-refractory of these toughener, small part can decompose again in 275-325 DEG C of extrusion process, cause its toughening effect to be not so good as
Ultra-fine fully vulcanized powder rubber is obvious like that, the performance of remaining performance composite also significantly lower than embodiment 1-6.
To sum up, the preparation method of ultra-fine fully vulcanized powder rubber toughness reinforcing high temperature resistant nylon composite material of the invention includes:First prepare
Plasticizing mother particle, then by each raw material according to proportioning mixing after, extruded, check rod and pelletizing obtain ultra-fine fully vulcanized powder rubber
Toughness reinforcing high temperature resistant nylon composite material.Wherein, because the particle diameter of ultra-fine fully vulcanized powder rubber particle is smaller, surface area is larger,
After high temperature resistant nylon resin is added into, " pseudo-crystalline lattice " distributed architecture is easily formed, it is possible in high temperature resistant nylon resin
Dispersed, this can not only increase substantially the toughness of the composite being finally made, moreover it is possible to composite is kept higher
Tensile strength and heat resisting temperature.
The above-mentioned description to embodiment is to be understood that and use the present invention for ease of those skilled in the art.It is familiar with
The personnel of art technology obviously can easily make various modifications to these embodiments, and should General Principle described herein
Use in other embodiment without by performing creative labour.Therefore, the invention is not restricted to above-described embodiment, art technology
Personnel's announcement of the invention, does not depart from improvement that scope made and modification all should be in protection scope of the present invention
Within.
Claims (10)
1. a kind of ultra-fine fully vulcanized powder rubber toughness reinforcing high temperature resistant nylon composite material, it is characterised in that:Comprising following components and respectively
The weight portion of component is as follows:
2. ultra-fine fully vulcanized powder rubber toughness reinforcing high temperature resistant nylon composite material according to claim 1, it is characterised in that:Institute
High temperature resistant nylon resin is stated for PA46, PA9T, PA10T, the PA6T and polyphthalamide of fusing point between 285-315 DEG C
In any one or a few.
3. ultra-fine fully vulcanized powder rubber toughness reinforcing high temperature resistant nylon composite material according to claim 1, it is characterised in that:Institute
State plasticizing mother particle and contain the high temperature resistant nylon resin and ultra-fine fully vulcanized powder rubber;
Preferably, the ultra-fine fully vulcanized powder rubber for it is ultra-fine it is full vulcanization butadiene-styrene rubber, it is ultra-fine it is full vulcanization carboxylic styrene-butadiene rubber,
Ultra-fine full vulcanized acrylate rubber, ultra-fine full-sulfurized nitrile rubber, ultra-fine full vulcanization XNBR and ultra-fine full silicon sulfide
Any one or a few in rubber.
4. ultra-fine fully vulcanized powder rubber toughness reinforcing high temperature resistant nylon composite material according to claim 3, it is characterised in that:Institute
The average grain diameter for stating ultra-fine full vulcanization butadiene-styrene rubber is 100nm;And/or,
The average grain diameter of the ultra-fine full vulcanization carboxylic styrene-butadiene rubber is 150nm;And/or,
The average grain diameter of the ultra-fine full vulcanized acrylate rubber is 150nm;And/or,
The average grain diameter of the ultra-fine full-sulfurized nitrile rubber is 100nm;And/or,
The average grain diameter of the ultra-fine full vulcanization XNBR is 50nm;And/or,
The average grain diameter of the ultra-fine full sulphurated siliastic is 100nm.
5. ultra-fine fully vulcanized powder rubber toughness reinforcing high temperature resistant nylon composite material according to claim 3, it is characterised in that:Institute
The weight ratio for stating the high temperature resistant nylon resin in plasticizing mother particle and ultra-fine fully vulcanized powder rubber is 1:1.
6., according to any described ultra-fine fully vulcanized powder rubber toughness reinforcing high temperature resistant nylon composite material in claim 1 to 5, it is special
Levy and be:The reinforcer is talcum powder, wollastonite, sepiolite, calcium carbonate, mica powder, glass microballoon and milled glass
Any one or a few in fiber;And/or,
The auxiliary agent be silane coupler, antioxidant, lubricant and nucleator in any one or a few.
7. ultra-fine fully vulcanized powder rubber toughness reinforcing high temperature resistant nylon composite material according to claim 6, it is characterised in that:Institute
Silane coupler is stated for N- β (aminoethyl)-γ-aminopropyltrimethoxysilane;And/or,
The weight portion of the silane coupler is 0-0.6 parts, when the weight portion of the reinforcer is 0, the silane coupler
Weight portion also be 0;And/or,
The antioxidant is N, N'- pairs-(3- (3,5- di-tert-butyl-hydroxy phenyls) propiono) hexamethylene diamine and the three (uncles of 2.4- bis-
Butyl phenyl) phosphite ester compounding;And/or,
The weight portion of the antioxidant is 0.3-0.6 parts;And/or,
The lubricant is any one in pentaerythritol stearate, calcium stearate or lithium stearate;And/or,
The weight portion of the lubricant is 0.2-0.7 parts;And/or,
The nucleator is Long carbon chain carboxylic acid calcium salt CVA102;And/or,
The weight portion of the nucleator is 0.01-0.05 parts.
8. a kind of ultra-fine fully vulcanized powder rubber toughness reinforcing high temperature resistant nylon composite material prepared as described in any in claim 1 to 7
Method, it is characterised in that comprise the following steps:
(1), by the dried high temperature resistant nylon resin of 25-75 weight portions, the dried plasticizing mother particle of 10-50 weight portions, 0-35
The reinforcer of weight portion and the auxiliary agent mixing of 0.51-1.95 weight portions, obtain compound;
(2), by the compound is extruded, check rod and pelletizing, obtain ultra-fine fully vulcanized powder rubber toughness reinforcing high temperature resistant nylon and answer
Condensation material.
9. method according to claim 8, it is characterised in that:The preparation method of the plasticizing mother particle comprises the following steps:
It is 1 according to weight ratio by dried high temperature resistant nylon resin and dried ultra-fine fully vulcanized powder rubber:1 ratio
Example is mixed, and melt blending and extruding pelletization obtain the plasticizing mother particle.
10. method according to claim 8, it is characterised in that:The time of the mixing in step (1) is 5 ± 5min;With/
Or,
Extrusion in step (2) is carried out in double screw extruder, and extrusion temperature is 275-325 DEG C, the double screw extruder
Feeding frequency be 10Hz, main-machine screw rotating speed be 300r/min.
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108003606A (en) * | 2017-12-12 | 2018-05-08 | 吴江市强塑阀门管件厂 | A kind of preparation method of ageing-resistant sewer pipe flat mouth sealing ring |
CN111334033A (en) * | 2020-04-22 | 2020-06-26 | 邵阳市宝晟环保科技有限公司 | Nylon material toughness auxiliary agent and preparation method thereof |
CN115011110A (en) * | 2022-06-20 | 2022-09-06 | 中广核俊尔(浙江)新材料有限公司 | PA6 carrier toughening master batch |
CN115819917A (en) * | 2022-12-22 | 2023-03-21 | 金发科技股份有限公司 | ABS composite material and preparation method and application thereof |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1381529A (en) * | 2001-04-18 | 2002-11-27 | 中国石油化工股份有限公司 | Full-sulfurized thermoplastic polyamide elastomer and its preparing process |
CN101191013A (en) * | 2006-11-21 | 2008-06-04 | 上海普利特复合材料有限公司 | Plasticizing enhancement nylon 6 composite material with good apparent mass and preparation method thereof |
CN101555351A (en) * | 2008-04-10 | 2009-10-14 | 上海杰事杰新材料股份有限公司 | Preparation method of nano rubber toughening nylon material |
CN101948617A (en) * | 2010-10-08 | 2011-01-19 | 苏州旭光聚合物有限公司 | Glass fiber/mineral composite reinforced modified nylon-6 material and preparation method thereof |
CN103834161A (en) * | 2012-11-26 | 2014-06-04 | 上海杰事杰新材料(集团)股份有限公司 | High-temperature resistant semi aromatic nylon composite material and preparation method thereof |
CN104231616A (en) * | 2013-06-07 | 2014-12-24 | 上海杰事杰新材料(集团)股份有限公司 | Reinforcing toughening high-temperature-resistant nylon composite material and preparation method thereof |
-
2015
- 2015-12-18 CN CN201510957772.9A patent/CN106893318A/en active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1381529A (en) * | 2001-04-18 | 2002-11-27 | 中国石油化工股份有限公司 | Full-sulfurized thermoplastic polyamide elastomer and its preparing process |
CN101191013A (en) * | 2006-11-21 | 2008-06-04 | 上海普利特复合材料有限公司 | Plasticizing enhancement nylon 6 composite material with good apparent mass and preparation method thereof |
CN101555351A (en) * | 2008-04-10 | 2009-10-14 | 上海杰事杰新材料股份有限公司 | Preparation method of nano rubber toughening nylon material |
CN101948617A (en) * | 2010-10-08 | 2011-01-19 | 苏州旭光聚合物有限公司 | Glass fiber/mineral composite reinforced modified nylon-6 material and preparation method thereof |
CN103834161A (en) * | 2012-11-26 | 2014-06-04 | 上海杰事杰新材料(集团)股份有限公司 | High-temperature resistant semi aromatic nylon composite material and preparation method thereof |
CN104231616A (en) * | 2013-06-07 | 2014-12-24 | 上海杰事杰新材料(集团)股份有限公司 | Reinforcing toughening high-temperature-resistant nylon composite material and preparation method thereof |
Non-Patent Citations (2)
Title |
---|
乔金梁: "超细橡胶粒子改性塑料的微观结构及其应用", 《现代化工·冶金·材料·能源 中国工程院化工、冶金与材料工程学部 第九届学术会议论文集(下册)》 * |
邓如生: "《共混改性工程塑料》", 31 July 2003, 化学工业出版社 * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108003606A (en) * | 2017-12-12 | 2018-05-08 | 吴江市强塑阀门管件厂 | A kind of preparation method of ageing-resistant sewer pipe flat mouth sealing ring |
CN111334033A (en) * | 2020-04-22 | 2020-06-26 | 邵阳市宝晟环保科技有限公司 | Nylon material toughness auxiliary agent and preparation method thereof |
CN115011110A (en) * | 2022-06-20 | 2022-09-06 | 中广核俊尔(浙江)新材料有限公司 | PA6 carrier toughening master batch |
CN115011110B (en) * | 2022-06-20 | 2024-04-26 | 中广核俊尔(浙江)新材料有限公司 | PA6 carrier toughening master batch |
CN115819917A (en) * | 2022-12-22 | 2023-03-21 | 金发科技股份有限公司 | ABS composite material and preparation method and application thereof |
CN115819917B (en) * | 2022-12-22 | 2024-03-22 | 金发科技股份有限公司 | ABS composite material and preparation method and application thereof |
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