CN108219433A - A kind of polyphenylene oxide resin alloy and preparation method thereof - Google Patents
A kind of polyphenylene oxide resin alloy and preparation method thereof Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
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Abstract
The present invention discloses a kind of polyphenylene oxide resin alloy and preparation method thereof, wherein, polyphenylene oxide resin alloy is composed of the following components：40 70 parts by weight of polyphenyleneoxide resins, 10 30 parts by weight diisocyanate compounds, 5 20 parts by weight terpene resins, 2 16 weight parts of elastomer, 1 10 parts by weight diene hydrocarbon oligomers, 38 parts by weight of flame retardant, 0.2 0.8 parts by weight antioxidant and 5 20 parts by weight grafts；The diene hydrocarbon oligomer that the diene polymerization average weight-molecular mass molecular weight obtained by the reaction that it is 46 by carbon atom number that the diene hydrocarbon oligomer, which is, is 1000 5000g/mol.The present invention improves the mobility and anti-flammability of polyphenylene oxide resin alloy on the basis of improving the resistance to Organic chemical solvents of polyphenylene oxide resin alloy and not reducing its heat resistance.
Description
Technical field
The present invention relates to resin alloy fields, are related specifically to a kind of polyphenylene oxide resin alloy and preparation method thereof.
Background technology
Polyphenylene oxide resin has many excellent performances, for example, mechanical performance, heat resistance, dimensional stability, from fire-retardant
Performance etc., alloy are widely used in the fields such as electronic apparatus, auto parts and components, communication photovoltaic.In recent years, polyphenylene oxide resin sheet
Body is more and more more and more universal for household appliance technical field, the particularly application in small household appliances field, but polyphenylene oxide resin sheet
The resistance to Organic chemical solvents of body are poor, particularly to grease type, easily generate stress cracking phenomenon, this just allows polyphenylene oxide alloy material
Expect that the application in this field is greatly limited, but existing polyphenylene oxide resin alloy improves its resistance to Organic chemical solvents
Property, but have ignored the impaired of its heat resistance and mobility and anti-flammability.
Invention content
In view of this, the purpose of the present invention is to provide a kind of polyphenylene oxide resin alloys and preparation method thereof, poly- improving
Resistance to Organic chemical solvents of phenylene ether resins alloy and on the basis of not reducing its heat resistance, improve polyphenylene oxide resin alloy
Mobility and anti-flammability.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：A kind of polyphenylene oxide resin alloy, by following
Component forms：40-70 parts by weight of polyphenyleneoxide resin, 10-30 parts by weight diisocyanate compound, 5-20 parts by weight terpenes trees
Fat, 2-16 weight parts of elastomer, 1-10 parts by weight diene hydrocarbon oligomer, 3-8 parts by weight of flame retardant, 0.2-0.8 parts by weight antioxygens
Agent and 5-20 parts by weight grafts；The diene hydrocarbon oligomer is obtained by the reaction for the diene polymerization for being 4-6 by carbon atom number
Average weight-molecular mass molecular weight is the diene hydrocarbon oligomer of 1000-5000g/mol.
Above-mentioned polyphenylene oxide resin alloy, the fire retardant are composed of the following components：10-30 parts by weight carboxylic carbon nano-tubes
Nano particle, 1-10 parts by weight ammonium polyphosphate, 2-6 parts by weight expansible graphite, 1-4 parts by weight of alumina nano particle and 0.5-
3 parts by weight of titanium dioxide nano particles.
Above-mentioned polyphenylene oxide resin alloy, the diene hydrocarbon oligomer is by 10-30 weight parts of butadiene oligomer, 10-30 weights
Measure part pentadiene oligomer and 10-30 parts by weight hexadienes oligomer composition.
Above-mentioned polyphenylene oxide resin alloy, the antioxidant by 0.5-2 parts by weight of lemon acid, 1-3 parts by weight tocopherol and
0.3-1.6 parts by weight phosphite ester forms.
Above-mentioned polyphenylene oxide resin alloy, the elastomer are alfin rubber, and the alfin rubber is by 10-20 parts by weight butylbenzene
Rubber and 20-30 parts by weight 1,4- butadiene-isoprene copolymer glues composition.
Above-mentioned polyphenylene oxide resin alloy, the diisocyanate compound are different by 20-30 parts by weight diphenyl methane two
Cyanate, 10-36 parts by weight dicyclohexyl methyl hydride diisocyanate and 10-20 parts by weight of toluene diisocyanate composition.
Above-mentioned polyphenylene oxide resin alloy, the graft are using ethylene-propylene-diene copolymer as base material, with Malaysia
One or more grafts for graft in acid anhydrides, acrylic acid and itaconic anhydride.
Above-mentioned polyphenylene oxide resin alloy, the ethylene-propylene-diene copolymer by ethylene, propylene and butadiene according to
The amount of substance is than 3:3:2 copolyreaction are made.
The preparation method of above-mentioned polyphenylene oxide resin alloy, includes the following steps：
1）Prepare raw material according to the following recipe：40-70 parts by weight of polyphenyleneoxide resin, 10-30 parts by weight diisocyanates chemical combination
Object, 5-20 parts by weight terpene resin, 2-16 weight parts of elastomer, 1-10 parts by weight diene hydrocarbon oligomer, 3-8 parts by weight are fire-retardant
Agent, 0.2-0.8 parts by weight antioxidant and 5-20 parts by weight grafts；
2）The polyphenylene oxide resin of graft and 50wt% is blended to obtain the first blend；By terpene resin and the polyphenylene oxide of 25wt%
Resin alloy obtains the second blend；The polyphenylene oxide resin of diisocyanate compound and remaining 25wt% is blended to obtain
Third blend；Elastomer and diene hydrocarbon oligomer are blended to obtain the 4th blend；
3）The 4th blend of first blend and 30wt% are blended to obtain the 5th blend；By the second blend and 35wt%
4th blend is blended to obtain the 6th blend；4th blend of third blend and 35wt% is blended to obtain the 7th blending
Object；
4）5th blend, the 6th blend, the 7th blend, fire retardant and antioxidant from main spout are added in successively and carried out
Mixed melting extruding pelletization.
Above-mentioned preparation method, step 4）Specially：By the 5th blend, the 6th blend, the 7th blend, fire retardant and
Antioxidant adds in successively from main spout, and then stirring at low speed mixes 10-20 minutes at normal temperatures, then in temperature 160-170
It DEG C is kneaded 20-30 minutes, then plasticate 5-8 minutes at 170-175 DEG C of temperature, then extruding pelletization.
Beneficial effects of the present invention are as follows：
The present invention using between diisocyanate compound, elastomer, diene hydrocarbon oligomer and graft reaction and
Graft copolymerization and cross-linking reaction between polyphenylene oxide resin improve the degree of cross linking inside polyphenylene oxide resin alloy, also improve
Compatible degree between polyphenylene oxide resin and diisocyanate compound and elastomer and diene hydrocarbon oligomer, and then improve
The uniformity of the performance of polyphenylene oxide resin alloy, at the same can also ensure in polyphenylene oxide resin alloy process mobility and
Heat resistance, and using carboxylic carbon nano-tube granular absorption alumina particle and titanium dioxide granule and be uniformly mixed the two
Afterwards, the synergistic effect between the two and expansible graphite is improved, and then improves the anti-flammability of polyphenylene oxide resin alloy.
Specific embodiment
In order to illustrate more clearly of the present invention, with reference to preferred embodiment, the present invention is described further.Ability
Field technique personnel should be appreciated that following specifically described content is illustrative and be not restrictive, this should not be limited with this
The protection domain of invention.
Embodiment 1
The present invention provides a kind of polyphenylene oxide resin alloy, composed of the following components：
40 parts by weight of polyphenyleneoxide resins；
30 parts by weight diisocyanate compounds, wherein, the diisocyanate compound is by 20 parts by weight diphenylmethyls
Alkane diisocyanate, 10 parts by weight dicyclohexyl methyl hydride diisocyanates and 10 parts by weight of toluene diisocyanate composition；
5 parts by weight terpene resins；
8 weight parts of elastomer, wherein, the elastomer is alfin rubber, the alfin rubber by 10 parts by weight butadiene-styrene rubber and
20 parts by weight 1,4- butadiene-isoprene copolymer glues form；
3 parts by weight diene hydrocarbon oligomers, wherein, the diene hydrocarbon oligomer is anti-for the diene polymerization for being 4-6 by carbon atom number
Diene hydrocarbon oligomer of the average weight-molecular mass molecular weight that should be obtained for 1000-5000g/mol, the diene hydrocarbon oligomer
It is made of 10 weight parts of butadiene oligomer, 10 parts by weight pentadiene oligomer and 10 parts by weight hexadiene oligomer；
4 parts by weight of flame retardant, wherein, the fire retardant is by 10 parts by weight carboxylic carbon nano-tube nano particles, the poly- phosphorus of 3 parts by weight
Sour ammonium, 2 parts by weight expansible graphites, 1.2 parts by weight of alumina nano particles and 0.5 parts by weight of titanium dioxide nano particle group
Into；The carboxylic carbon nano-tube nano particle is carboxylated single-layer carbon nano-tube nano particle；
0.3 parts by weight antioxidant, wherein, the antioxidant is by 0.7 parts by weight of lemon acid, 1 parts by weight tocopherol and 0.5 parts by weight
Phosphite ester forms；
10 parts by weight grafts, wherein, the graft is using ethylene-propylene-diene copolymer as base material, with maleic acid
One or more grafts for graft in acid anhydride, acrylic acid and itaconic anhydride, the ethylene-propylene-diene copolymer
By ethylene, propylene and butadiene according to the amount ratio 3 of substance:3:2 copolyreaction are made, the maleic anhydride, the acrylic acid and
The weight ratio of the itaconic anhydride is：1:2:3.
The preparation method of above-mentioned polyphenylene oxide resin alloy, includes the following steps：
1）Prepare raw material according to above-mentioned formula；
2）The polyphenylene oxide resin of graft and 50wt% is blended to obtain the first blend；By terpene resin and the polyphenylene oxide of 25wt%
Resin alloy obtains the second blend；The polyphenylene oxide resin of diisocyanate compound and remaining 25wt% is blended to obtain
Third blend；Elastomer and diene hydrocarbon oligomer are blended to obtain the 4th blend；
3）The 4th blend of first blend and 30wt% are blended to obtain the 5th blend；By the second blend and 35wt%
4th blend is blended to obtain the 6th blend；4th blend of third blend and 35wt% is blended to obtain the 7th blending
Object；
4）5th blend, the 6th blend, the 7th blend, fire retardant and antioxidant will be added in successively from main spout,
Then stirring at low speed mixes 10-20 minutes at normal temperatures, then in mixing 20-30 minutes of 160-170 DEG C of temperature, then in temperature
It plasticates at 170-175 DEG C 5-8 minutes, then extruding pelletization, obtained polyphenylene oxide resin alloy is denoted as alloy 1.
Embodiment 2
The present invention provides a kind of polyphenylene oxide resin alloy, composed of the following components：
50 parts by weight of polyphenyleneoxide resins；
20 parts by weight diisocyanate compounds, wherein, the diisocyanate compound is by 20 parts by weight diphenylmethyls
Alkane diisocyanate, 18 parts by weight dicyclohexyl methyl hydride diisocyanates and 10 parts by weight of toluene diisocyanate composition；
10 parts by weight terpene resins；
12 weight parts of elastomer, wherein, the elastomer is alfin rubber, the alfin rubber by 10 parts by weight butadiene-styrene rubber and
30 parts by weight 1,4- butadiene-isoprene copolymer glues form；
6 parts by weight diene hydrocarbon oligomers, wherein, the diene hydrocarbon oligomer is anti-for the diene polymerization for being 4-6 by carbon atom number
Diene hydrocarbon oligomer of the average weight-molecular mass molecular weight that should be obtained for 1000-5000g/mol, the diene hydrocarbon oligomer
It is made of 10 weight parts of butadiene oligomer, 20 parts by weight pentadiene oligomer and 10 parts by weight hexadiene oligomer；
6 parts by weight of flame retardant, wherein, the fire retardant is by 15 parts by weight carboxylic carbon nano-tube nano particles, the poly- phosphorus of 6 parts by weight
Sour ammonium, 2.4 parts by weight expansible graphites, 1.6 parts by weight of alumina nano particles and 1.2 parts by weight of titanium dioxide nano particle groups
Into；The carboxylic carbon nano-tube nano particle is carboxylated multilayer carbon nanotube nano particle；
0.5 parts by weight antioxidant, wherein, the antioxidant is by 0.9 parts by weight of lemon acid, 1.4 parts by weight tocopherols and 0.3 weight
Part phosphite ester composition；
12 parts by weight grafts, wherein, the graft is using ethylene-propylene-diene copolymer as base material, with maleic acid
One or more grafts for graft in acid anhydride, acrylic acid and itaconic anhydride, the ethylene-propylene-diene copolymer
By ethylene, propylene and butadiene according to the amount ratio 3 of substance:3:2 copolyreaction are made, the maleic anhydride, the acrylic acid and
The weight ratio of the itaconic anhydride is：2:3:1.
The preparation method of polyphenylene oxide resin alloy and the preparation method of polyphenylene oxide resin alloy in embodiment 1 in the present embodiment
Identical, polyphenylene oxide resin alloy obtained is denoted as alloy 2 in the present embodiment.
Embodiment 3
The present invention provides a kind of polyphenylene oxide resin alloy, composed of the following components：
60 parts by weight of polyphenyleneoxide resins；
30 parts by weight diisocyanate compounds, wherein, the diisocyanate compound is by 20 parts by weight diphenylmethyls
Alkane diisocyanate, 36 parts by weight dicyclohexyl methyl hydride diisocyanates and 10 parts by weight of toluene diisocyanate composition；
15 parts by weight terpene resins；
6 weight parts of elastomer, wherein, the elastomer is alfin rubber, the alfin rubber by 20 parts by weight butadiene-styrene rubber and
20 parts by weight 1,4- butadiene-isoprene copolymer glues form；
8 parts by weight diene hydrocarbon oligomers, wherein, the diene hydrocarbon oligomer is anti-for the diene polymerization for being 4-6 by carbon atom number
Diene hydrocarbon oligomer of the average weight-molecular mass molecular weight that should be obtained for 1000-5000g/mol, the diene hydrocarbon oligomer
It is made of 10 weight parts of butadiene oligomer, 30 parts by weight pentadiene oligomer and 10 parts by weight hexadiene oligomer；
8 parts by weight of flame retardant, wherein, the fire retardant is by 25 parts by weight carboxylic carbon nano-tube nano particles, the poly- phosphorus of 8 parts by weight
Sour ammonium, 4 parts by weight expansible graphites, 2.3 parts by weight of alumina nano particles and 2.1 parts by weight of titanium dioxide nano particle groups
Into；The carboxylic carbon nano-tube nano particle is carboxylated single-layer carbon nano-tube nano particle；
0.8 parts by weight antioxidant, wherein, the antioxidant is by 1.5 parts by weight of lemon acid, 1.9 parts by weight tocopherols and 0.9 weight
Part phosphite ester composition；
16 parts by weight grafts, wherein, the graft is using ethylene-propylene-diene copolymer as base material, with maleic acid
One or more grafts for graft in acid anhydride, acrylic acid and itaconic anhydride, the ethylene-propylene-diene copolymer
By ethylene, propylene and butadiene according to the amount ratio 3 of substance:3:2 copolyreaction are made, the maleic anhydride, the acrylic acid and
The weight ratio of the itaconic anhydride is：1:1:1.
The preparation method of polyphenylene oxide resin alloy and the preparation method of polyphenylene oxide resin alloy in embodiment 1 in the present embodiment
Identical, polyphenylene oxide resin alloy obtained is denoted as alloy 3 in the present embodiment.
Embodiment 4
The present invention provides a kind of polyphenylene oxide resin alloy, composed of the following components：
70 parts by weight of polyphenyleneoxide resins；
20 parts by weight diisocyanate compounds, wherein, the diisocyanate compound is by 20 parts by weight diphenylmethyls
Alkane diisocyanate, 36 parts by weight dicyclohexyl methyl hydride diisocyanates and 20 parts by weight of toluene diisocyanate composition；
20 parts by weight terpene resins；
9 weight parts of elastomer, wherein, the elastomer is alfin rubber, the alfin rubber by 20 parts by weight butadiene-styrene rubber and
30 parts by weight 1,4- butadiene-isoprene copolymer glues form；
10 parts by weight diene hydrocarbon oligomers, wherein, the diene hydrocarbon oligomer is anti-for the diene polymerization for being 4-6 by carbon atom number
Diene hydrocarbon oligomer of the average weight-molecular mass molecular weight that should be obtained for 1000-5000g/mol, the diene hydrocarbon oligomer
It is made of 10 weight parts of butadiene oligomer, 20 parts by weight pentadiene oligomer and 20 parts by weight hexadiene oligomer；
3 parts by weight of flame retardant, wherein, the fire retardant is gathered by 30 parts by weight carboxylic carbon nano-tube nano particles, 10 parts by weight
Ammonium phosphate, 4.2 parts by weight expansible graphites, 3.5 parts by weight of alumina nano particles and 3 parts by weight of titanium dioxide nano particle groups
Into；The carboxylic carbon nano-tube nano particle is carboxylated multilayer carbon nanotube nano particle；
0.2 parts by weight antioxidant, wherein, the antioxidant is by 2 parts by weight of lemon acid, 2.6 parts by weight tocopherols and 1.3 parts by weight
Phosphite ester forms；
5 parts by weight grafts, wherein, the graft be using ethylene-propylene-diene copolymer as base material, with maleic anhydride,
One or more grafts for graft in acrylic acid and itaconic anhydride, the ethylene-propylene-diene copolymer is by second
Alkene, propylene and butadiene according to substance amount ratio 3:3:2 copolyreaction are made, the maleic anhydride, the acrylic acid and described
The weight ratio of itaconic anhydride is：3:2:2.
The preparation method of polyphenylene oxide resin alloy and the preparation method of polyphenylene oxide resin alloy in embodiment 1 in the present embodiment
Identical, polyphenylene oxide resin alloy obtained is denoted as alloy 4 in the present embodiment.
Embodiment 5
The present invention provides a kind of polyphenylene oxide resin alloy, composed of the following components：
40 parts by weight of polyphenyleneoxide resins；
10 parts by weight diisocyanate compounds, wherein, the diisocyanate compound is by 30 parts by weight diphenylmethyls
Alkane diisocyanate, 36 parts by weight dicyclohexyl methyl hydride diisocyanates and 20 parts by weight of toluene diisocyanate composition；
15 parts by weight terpene resins；
14 weight parts of elastomer, wherein, the elastomer is alfin rubber, the alfin rubber by 15 parts by weight butadiene-styrene rubber and
25 parts by weight 1,4- butadiene-isoprene copolymer glues form；
1 parts by weight diene hydrocarbon oligomer, wherein, the diene hydrocarbon oligomer is anti-for the diene polymerization for being 4-6 by carbon atom number
Diene hydrocarbon oligomer of the average weight-molecular mass molecular weight that should be obtained for 1000-5000g/mol, the diene hydrocarbon oligomer
It is made of 10 weight parts of butadiene oligomer, 20 parts by weight pentadiene oligomer and 30 parts by weight hexadiene oligomer；
5 parts by weight of flame retardant, wherein, the fire retardant is by 18 parts by weight carboxylic carbon nano-tube nano particles, the poly- phosphorus of 7 parts by weight
Sour ammonium, 5 parts by weight expansible graphites, 4 parts by weight of alumina nano particles and 1.6 parts by weight of titanium dioxide nano particles composition；
The carboxylic carbon nano-tube nano particle is carboxylated single-layer carbon nano-tube nano particle；
0.4 parts by weight antioxidant, wherein, the antioxidant is by 0.5 parts by weight of lemon acid, 1.3 parts by weight tocopherols and 1.6 weight
Part phosphite ester composition；
8 parts by weight grafts, wherein, the graft be using ethylene-propylene-diene copolymer as base material, with maleic anhydride,
One or more grafts for graft in acrylic acid and itaconic anhydride, the ethylene-propylene-diene copolymer is by second
Alkene, propylene and butadiene according to substance amount ratio 3:3:2 copolyreaction are made, the maleic anhydride, the acrylic acid and described
The weight ratio of itaconic anhydride is：3:1:1.
The preparation method of polyphenylene oxide resin alloy and the preparation method of polyphenylene oxide resin alloy in embodiment 1 in the present embodiment
Identical, polyphenylene oxide resin alloy obtained is denoted as alloy 5 in the present embodiment.
Embodiment 6
The present invention provides a kind of polyphenylene oxide resin alloy, composed of the following components：
50 parts by weight of polyphenyleneoxide resins；
30 parts by weight diisocyanate compounds, wherein, the diisocyanate compound is by 30 parts by weight diphenylmethyls
Alkane diisocyanate, 18 parts by weight dicyclohexyl methyl hydride diisocyanates and 20 parts by weight of toluene diisocyanate composition；
20 parts by weight terpene resins；
16 weight parts of elastomer, wherein, the elastomer is alfin rubber, the alfin rubber by 18 parts by weight butadiene-styrene rubber and
24 parts by weight 1,4- butadiene-isoprene copolymer glues form；
5 parts by weight diene hydrocarbon oligomers, wherein, the diene hydrocarbon oligomer is anti-for the diene polymerization for being 4-6 by carbon atom number
Diene hydrocarbon oligomer of the average weight-molecular mass molecular weight that should be obtained for 1000-5000g/mol, the diene hydrocarbon oligomer
It is made of 10 weight parts of butadiene oligomer, 30 parts by weight pentadiene oligomer and 30 parts by weight hexadiene oligomer；
7 parts by weight of flame retardant, wherein, the fire retardant is by 24 parts by weight carboxylic carbon nano-tube nano particles, the poly- phosphorus of 9 parts by weight
Sour ammonium, 6 parts by weight expansible graphites, 1 parts by weight of alumina nano particle and 2.4 parts by weight of titanium dioxide nano particles composition；
The carboxylic carbon nano-tube nano particle is carboxylated multilayer carbon nanotube nano particle；
0.7 parts by weight antioxidant, wherein, the antioxidant is by 1.3 parts by weight of lemon acid, 1.6 parts by weight tocopherols and 1.2 weight
Part phosphite ester composition；
20 parts by weight grafts, wherein, the graft is using ethylene-propylene-diene copolymer as base material, with maleic acid
One or more grafts for graft in acid anhydride, acrylic acid and itaconic anhydride, the ethylene-propylene-diene copolymer
By ethylene, propylene and butadiene according to the amount ratio 3 of substance:3:2 copolyreaction are made, the maleic anhydride, the acrylic acid and
The weight ratio of the itaconic anhydride is：2:1:1.
The preparation method of polyphenylene oxide resin alloy and the preparation method of polyphenylene oxide resin alloy in embodiment 1 in the present embodiment
Identical, polyphenylene oxide resin alloy obtained is denoted as alloy 6 in the present embodiment.
Embodiment 7
The present invention provides a kind of polyphenylene oxide resin alloy, composed of the following components：
60 parts by weight of polyphenyleneoxide resins；
20 parts by weight diisocyanate compounds, wherein, the diisocyanate compound is by 30 parts by weight diphenylmethyls
Alkane diisocyanate, 10 parts by weight dicyclohexyl methyl hydride diisocyanates and 15 parts by weight of toluene diisocyanate composition；
5 parts by weight terpene resins；
2 weight parts of elastomer, wherein, the elastomer is alfin rubber, the alfin rubber by 16 parts by weight butadiene-styrene rubber and
20 parts by weight 1,4- butadiene-isoprene copolymer glues form；
9 parts by weight diene hydrocarbon oligomers, wherein, the diene hydrocarbon oligomer is anti-for the diene polymerization for being 4-6 by carbon atom number
Diene hydrocarbon oligomer of the average weight-molecular mass molecular weight that should be obtained for 1000-5000g/mol, the diene hydrocarbon oligomer
It is made of 20 weight parts of butadiene oligomer, 30 parts by weight pentadiene oligomer and 30 parts by weight hexadiene oligomer；
4.8 parts by weight of flame retardant, wherein, the fire retardant is gathered by 16 parts by weight carboxylic carbon nano-tube nano particles, 1 parts by weight
Ammonium phosphate, 3.5 parts by weight expansible graphites, 1.8 parts by weight of alumina nano particles and 1.7 parts by weight of titanium dioxide nano particles
Composition；The carboxylic carbon nano-tube nano particle is carboxylated single-layer carbon nano-tube nano particle；
0.6 parts by weight antioxidant, wherein, the antioxidant is by 1.6 parts by weight of lemon acid, 2.5 parts by weight tocopherols and 0.8 weight
Part phosphite ester composition；
14 parts by weight grafts, wherein, the graft is using ethylene-propylene-diene copolymer as base material, with maleic acid
One or more grafts for graft in acid anhydride, acrylic acid and itaconic anhydride, the ethylene-propylene-diene copolymer
By ethylene, propylene and butadiene according to the amount ratio 3 of substance:3:2 copolyreaction are made, the maleic anhydride, the acrylic acid and
The weight ratio of the itaconic anhydride is：1:3:2.
The preparation method of polyphenylene oxide resin alloy and the preparation method of polyphenylene oxide resin alloy in embodiment 1 in the present embodiment
Identical, polyphenylene oxide resin alloy obtained is denoted as alloy 7 in the present embodiment.
Embodiment 8
The present invention provides a kind of polyphenylene oxide resin alloy, composed of the following components：
70 parts by weight of polyphenyleneoxide resins；
30 parts by weight diisocyanate compounds, wherein, the diisocyanate compound is by 30 parts by weight diphenylmethyls
Alkane diisocyanate, 36 parts by weight dicyclohexyl methyl hydride diisocyanates and 10 parts by weight of toluene diisocyanate composition；
15 parts by weight terpene resins；
10 weight parts of elastomer, wherein, the elastomer is alfin rubber, the alfin rubber by 10 parts by weight butadiene-styrene rubber and
25 parts by weight 1,4- butadiene-isoprene copolymer glues form；
4 parts by weight diene hydrocarbon oligomers, wherein, the diene hydrocarbon oligomer is anti-for the diene polymerization for being 4-6 by carbon atom number
Diene hydrocarbon oligomer of the average weight-molecular mass molecular weight that should be obtained for 1000-5000g/mol, the diene hydrocarbon oligomer
It is made of 30 weight parts of butadiene oligomer, 20 parts by weight pentadiene oligomer and 20 parts by weight hexadiene oligomer；
3.6 parts by weight of flame retardant, wherein, the fire retardant is gathered by 28 parts by weight carboxylic carbon nano-tube nano particles, 4 parts by weight
Ammonium phosphate, 3 parts by weight expansible graphites, 3.2 parts by weight of alumina nano particles and 0.9 parts by weight of titanium dioxide nano particle group
Into；The carboxylic carbon nano-tube nano particle is carboxylated multilayer carbon nanotube nano particle；
0.5 parts by weight antioxidant, wherein, the antioxidant is by 1.9 parts by weight of lemon acid, 2.8 parts by weight tocopherols and 1.1 weight
Part phosphite ester composition；
13 parts by weight grafts, wherein, the graft is using ethylene-propylene-diene copolymer as base material, with maleic acid
One or more grafts for graft in acid anhydride, acrylic acid and itaconic anhydride, the ethylene-propylene-diene copolymer
By ethylene, propylene and butadiene according to the amount ratio 3 of substance:3:2 copolyreaction are made, the maleic anhydride, the acrylic acid and
The weight ratio of the itaconic anhydride is：3:2:3.
The preparation method of polyphenylene oxide resin alloy and the preparation method of polyphenylene oxide resin alloy in embodiment 1 in the present embodiment
Identical, polyphenylene oxide resin alloy obtained is denoted as alloy 8 in the present embodiment.
Embodiment 9
The present invention provides a kind of polyphenylene oxide resin alloy, composed of the following components：
56 parts by weight of polyphenyleneoxide resins；
25 parts by weight diisocyanate compounds, wherein, the diisocyanate compound is by 26 parts by weight diphenylmethyls
Alkane diisocyanate, 18 parts by weight dicyclohexyl methyl hydride diisocyanates and 16 parts by weight of toluene diisocyanate composition；
18 parts by weight terpene resins；
12 weight parts of elastomer, wherein, the elastomer is alfin rubber, the alfin rubber by 20 parts by weight butadiene-styrene rubber and
24 parts by weight 1,4- butadiene-isoprene copolymer glues form；
8 parts by weight diene hydrocarbon oligomers, wherein, the diene hydrocarbon oligomer is anti-for the diene polymerization for being 4-6 by carbon atom number
Diene hydrocarbon oligomer of the average weight-molecular mass molecular weight that should be obtained for 1000-5000g/mol, the diene hydrocarbon oligomer
It is made of 25 weight parts of butadiene oligomer, 15 parts by weight pentadiene oligomer and 10 parts by weight hexadiene oligomer；
5.9 parts by weight of flame retardant, wherein, the fire retardant is by 17 parts by weight carboxylic carbon nano-tube nano particles, 7.5 parts by weight
Ammonium polyphosphate, 3.6 parts by weight expansible graphites, 2.4 parts by weight of alumina nano particles and 1.5 parts by weight of titanium dioxide nanometers
Grain composition；The carboxylic carbon nano-tube nano particle is by carboxylated single-layer carbon nano-tube nano particle and carboxylated multilayer carbon
Nano-tube nano particle is 2 according to mass ratio:3 mixtures being obtained by mixing；
0.57 parts by weight antioxidant, wherein, the antioxidant is by 1.2 parts by weight of lemon acid, 2.4 parts by weight tocopherols and 1.1 weights
Measure part phosphite ester composition；
18 parts by weight grafts, wherein, the graft is using ethylene-propylene-diene copolymer as base material, with maleic acid
One or more grafts for graft in acid anhydride, acrylic acid and itaconic anhydride, the ethylene-propylene-diene copolymer
By ethylene, propylene and butadiene according to the amount ratio 3 of substance:3:2 copolyreaction are made, the maleic anhydride, the acrylic acid and
The weight ratio of the itaconic anhydride is：5:4:3.
The preparation method of polyphenylene oxide resin alloy and the preparation method of polyphenylene oxide resin alloy in embodiment 1 in the present embodiment
Identical, polyphenylene oxide resin alloy obtained is denoted as alloy 9 in the present embodiment.
Comparative example
Polyphenylene oxide resin alloy is composed of the following components in the present embodiment：45 parts by weight of polyphenyleneoxide resins, 31.7 parts by weight nylon
Resin, 1 weight parts of elastomer, 8 parts by weight of flame retardant, 1 parts by weight polyolefin, 7 parts by weight grafts, 5 parts by weight functional master batch,
1 parts by weight black masterbatch, 0.2 parts by weight antioxidant, 0.1 parts by weight auxiliary anti-oxidant, wherein, polyphenylene oxide resin 2,6- dimethyl benzenes
The copolymer of the polymer of phenol, 2,6- xylenols and 2,3,6-TMP, inherent viscosity 0.2-0.6dl/g,
The nylon resin selects one or two kinds of mixture in nylon 6 or nylon66 fiber, and the elastomer is preferably poly- fourth
Diene, neoprene, isoprene rubber, trans-polyisoprene, butadiene-styrene rubber, hydrogenated styrene-butadiene rubber, hydrogenation nitrile rubber, second third
At least one of rubber, ethylene copolymer, the polyolefin is polyethylene, polypropylene, poly 1-butene, poly- 4- methyl-1-pentenes
At least one of alkene, ethylene-propylene copolymer, ethylene-butene copolymer, the fire retardant are by phosphorus flame retardant, nitrogen system
The flame-retardant system that fire retardant, inorganic hydroxide are combined, the weight ratio of three is (1~3):(1~2):(1~2).Its
In, phosphorus flame retardant is triphenyl phosphate (TPP), tetraphenyl (bisphenol-A) bisphosphate (BDP), two phosphorus of tetraphenyl resorcinol
One or several kinds of mixtures in acid esters (RDP), fragrant alkene condensed phosphoric acid esters (PX-200), encapsulated red phosphorus；Nitrogenated flame retardant
For in melamine, melamine cyanurate at least one of；Inorganic hydroxide is aluminium hydroxide, in magnesium hydroxide
At least one, the functional master batch are had inorganic microporous material, the 4- of diatom structure by 60-90wt% resin matrixes, 3-18wt%
18 organic inorganic hybridization mesoporous materials and 3-10wt% lubricants, the resin matrix is polyphenylene oxide resin, nylon resin, elasticity
At least one of body, polyolefin；The graft is with polyphenylene oxide resin, nylon resin, butadiene-styrene rubber, hydrogenation butylbenzene rubber
At least one of glue, ethylene-propylene copolymer are base material, at least one in maleic anhydride, itaconic anhydride, citric acid
Kind is graft.
The preparation method of polyphenylene oxide resin alloy is with reference to the preparation side of polyphenylene oxide resin alloy in embodiment 1 in the present embodiment
Method, polyphenylene oxide resin alloy obtained are denoted as comparative alloy.
Performance test：
Polyphenylene oxide prepared by polyphenylether resin alloy material and comparison example prepared by above-described embodiment 1 to embodiment 9
Resin alloy material is carried out respectively such as the performance test in table 1.Correlated performance test method is as follows：
（1）Tensile strength：The tensile strength is tested by ASTM D-638.
（2）Bending strength：The bending strength is tested by ASTM D-790.
（3）Bending modulus：The bending strength is tested by ASTM D-790.
(4) Izod notch shocks：The Izod notch shocks are tested by ASTM D-256.
(5) heat distortion temperature：The heat distortion temperature is hit is tested by ASTM D-648.
(6) anti-flammability：The anti-flammability presses UL-94 standard testings.
(7) punching experiment：The punching experiment, is fixed on fixture in Injection moulded part, makes a call to diameter 5mm, a thickness
For the aperture of 32mm, it is qualification that product is not cracking in whole process is punched, if cracking, is considered as unqualified.
(8) grease resistance is tested：The grease resistance experiment is after punching is tested, one is coated around product punching
Into grease (natural oil or Synthetic Oil), stationary sample 24~72 hours such as not cracking phenomenon, is then considered as qualification,
Conversely, it is unqualified.
After tested, above-described embodiment 1 to embodiment 9 and comparison example material correlated performance is shown in Table 1.
The performance test results of 1 alloy 1-9 of table and comparative alloy
| Comparative alloy | Alloy 1 | Alloy 2 | Alloy 3 | Alloy 4 | Alloy 5 | Alloy 6 | Alloy 7 | Alloy 8 | Alloy 9 | |
| Tensile strength（MPa） | 57.2 | 278 | 312 | 392 | 374 | 362 | 386 | 346 | 356 | 398 |
| Bending strength（MPa） | 82 | 516 | 607 | 647 | 635 | 586 | 642 | 594 | 617 | 658 |
| Bending modulus（MPa） | 2244 | 3208 | 3928 | 4396 | 4306 | 4138 | 4318 | 3807 | 4126 | 4437 |
| 23 DEG C of cantilever beam notch strengths（KJ/M2） | 52.5 | 82 | 85 | 95 | 92 | 87 | 98 | 89 | 91 | 106 |
| Thermal denaturation temperature（1.82MPa） | 91 | 94 | 103 | 112 | 113 | 96 | 110 | 99 | 106 | 116 |
| Flame retardant rating | V1 | V1 | V1 | V0 | V1 | V0 | V0 | V1 | V1 | V0 |
| Punching experiment | It is qualified | It is qualified | It is qualified | It is qualified | It is qualified | It is qualified | It is qualified | It is qualified | It is qualified | It is qualified |
| Grease resistance is tested | It is qualified | It is qualified | It is qualified | It is qualified | It is qualified | It is qualified | It is qualified | It is qualified | It is qualified | It is qualified |
By the data in table 1 it is found that with carboxylic carbon nano-tube nano particle dosage increase, polyphenylene oxide resin alloy it is fire-retardant
Performance and mechanical performance all increased, and reason is that carboxylic carbon nano-tube can be with adsorption and oxidation aluminum nanoparticles and dioxy
Change titanium nano particle, reduce aluminum oxide nanoparticle and titania nanoparticles agglomeration, be conducive to increase metal oxygen
Synergistic effect between compound and expansible graphite and ammonium polyphosphate improves the flame retardant property of polyphenylene oxide resin, and carboxyl
Carboxyl on carbon nano tube nano particle can react with the functional group in acrylic acid, maleic anhydride and itaconic anhydride,
Improve polyphenylene oxide resin, diisocyanate compound, terpene resin, diene hydrocarbon oligomer, elasticity in polyphenylene oxide resin alloy
Compatible degree between body and graft improves the uniformity of the mechanical performance of polyphenylene oxide resin alloy in the present invention, alkadienes
The addition of oligomer is conducive to improve the degree of cross linking of polyphenylene oxide resin alloy and polyphenylene oxide resin, diisocyanates chemical combination
Object, terpene resin, graft and elastomer compatibility and the present invention in polyphenylene oxide resin alloy impact strength.
The above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be to the present invention
Embodiment restriction, for those of ordinary skill in the art, can also make on the basis of the above description
Other various forms of variations or variation here can not be exhaustive all embodiments, every skill for belonging to the present invention
The obvious changes or variations that art scheme is extended out are still in the row of protection scope of the present invention.
Claims (10)
1. a kind of polyphenylene oxide resin alloy, which is characterized in that composed of the following components：40-70 parts by weight of polyphenyleneoxide resin, 10-
30 parts by weight diisocyanate compounds, 5-20 parts by weight terpene resin, 2-16 weight parts of elastomer, 1-10 parts by weight diene
Hydrocarbon oligomer, 3-8 parts by weight of flame retardant, 0.2-0.8 parts by weight antioxidant and 5-20 parts by weight grafts；The alkadienes is oligomeric
Object is 1000-5000g/ for the diene polymerization average weight-molecular mass molecular weight obtained by the reaction for being 4-6 by carbon atom number
The diene hydrocarbon oligomer of mol.
2. polyphenylene oxide resin alloy according to claim 1, which is characterized in that the fire retardant is composed of the following components：
10-30 parts by weight carboxylic carbon nano-tubes nano particle, 1-10 parts by weight ammonium polyphosphate, 2-6 parts by weight expansible graphite, 1-4
Parts by weight of alumina nano particle and 0.5-3 parts by weight of titanium dioxide nano particles.
3. polyphenylene oxide resin alloy according to claim 1, which is characterized in that the diene hydrocarbon oligomer is by 10-30 weights
Measure part butadiene oligomer, 10-30 parts by weight pentadiene oligomer and 10-30 parts by weight hexadienes oligomer composition.
4. polyphenylene oxide resin alloy according to claim 1, which is characterized in that the antioxidant is by 0.5-2 parts by weight lemons
Lemon acid, 1-3 parts by weight tocopherol and 0.3-1.6 parts by weight phosphite ester composition.
5. polyphenylene oxide resin alloy according to claim 1, which is characterized in that the elastomer is alfin rubber, described
Alfin rubber is made of 10-20 parts by weight butadiene-styrene rubber and 20-30 parts by weight 1,4- butadiene-isoprene copolymer glues.
6. polyphenylene oxide resin alloy according to claim 1, which is characterized in that the diisocyanate compound by
20-30 parts by weight methyl diphenylene diisocyanate, 10-36 parts by weight dicyclohexyl methyl hydride diisocyanate and 10-20 weight
Part toluene di-isocyanate(TDI) composition.
7. according to any polyphenylene oxide resin alloys of claim 1-6, which is characterized in that the graft be with ethylene-
Propylene-butadiene copolymer is base material, with one or more connecing for graft in maleic anhydride, acrylic acid and itaconic anhydride
Branch body.
8. polyphenylene oxide resin alloy according to claim 7, which is characterized in that the ethylene-propylene-diene copolymer
By ethylene, propylene and butadiene according to the amount ratio 3 of substance:3:2 copolyreaction are made.
9. the preparation method of polyphenylene oxide resin alloy according to any one of claims 1-8, which is characterized in that including walking as follows
Suddenly：
1）Prepare raw material according to the following recipe：40-70 parts by weight of polyphenyleneoxide resin, 10-30 parts by weight diisocyanates chemical combination
Object, 5-20 parts by weight terpene resin, 2-16 weight parts of elastomer, 1-10 parts by weight diene hydrocarbon oligomer, 3-8 parts by weight are fire-retardant
Agent, 0.2-0.8 parts by weight antioxidant and 5-20 parts by weight grafts；
2）The polyphenylene oxide resin of graft and 50wt% is blended to obtain the first blend；By terpene resin and the polyphenylene oxide of 25wt%
Resin alloy obtains the second blend；The polyphenylene oxide resin of diisocyanate compound and remaining 25wt% is blended to obtain
Third blend；Elastomer and diene hydrocarbon oligomer are blended to obtain the 4th blend；
3）The 4th blend of first blend and 30wt% are blended to obtain the 5th blend；By the second blend and 35wt%
4th blend is blended to obtain the 6th blend；4th blend of third blend and 35wt% is blended to obtain the 7th blending
Object；
4）5th blend, the 6th blend, the 7th blend, fire retardant and antioxidant from main spout are added in successively and carried out
Mixed melting extruding pelletization.
10. the preparation method of polyphenylene oxide resin alloy according to claim 9, which is characterized in that step 4）Specially：It will
5th blend, the 6th blend, the 7th blend, fire retardant and antioxidant add in successively from main spout, then in room temperature
Lower stirring at low speed mixes 10-20 minutes, then in mixing 20-30 minutes of 160-170 DEG C of temperature, then at 170-175 DEG C of temperature
It plasticates 5-8 minutes, then extruding pelletization.
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| CN103497441A (en) * | 2013-10-12 | 2014-01-08 | 苏州市沃特新材料科技有限公司 | Polyphenyl ether resin alloy material, and preparation method and application thereof |
| CN104910604A (en) * | 2015-07-15 | 2015-09-16 | 上海锦湖日丽塑料有限公司 | Matt polycarbonate styrene resin alloy and preparation method thereof |
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| CN103497441A (en) * | 2013-10-12 | 2014-01-08 | 苏州市沃特新材料科技有限公司 | Polyphenyl ether resin alloy material, and preparation method and application thereof |
| CN104910604A (en) * | 2015-07-15 | 2015-09-16 | 上海锦湖日丽塑料有限公司 | Matt polycarbonate styrene resin alloy and preparation method thereof |
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