CN107286424A - A kind of high withstand voltage cross-linking radiation environmental protection flame retardant composite rubber-plastic material and preparation method thereof - Google Patents
A kind of high withstand voltage cross-linking radiation environmental protection flame retardant composite rubber-plastic material and preparation method thereof Download PDFInfo
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- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
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- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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Abstract
The present invention relates to a kind of high withstand voltage cross-linking radiation environmental protection flame retardant composite rubber-plastic material and preparation method thereof, by weight, the composition of raw materials of the composite includes：15 ~ 45 parts of high density polyethylene (HDPE)；25 ~ 50 parts of elastomer resin；EBA10 ~ 30 part；5 ~ 25 parts of toughener；60 ~ 100 parts of fire retardant；0.8 ~ 2 part of antioxidant；1 ~ 2 part of lubricant；0.03 ~ 0.1 part of crosslinking agent；1 ~ 2.5 part of crosslinking sensitizer；Wherein, elastomer resin includes polyurethane elastomer and ethylene-propylene-diene monomer glue elastomer, and the mass ratio of polyurethane elastomer and ethylene-propylene-diene monomer glue elastomer is 1：1~3.The present invention is formulated by improving, elastomer resin is such as used as using polyurethane elastomer and ethylene-propylene-diene monomer glue elastomer, add high density polyethylene (HDPE), EBA, the materials such as addition toughener, fire retardant, antioxidant are aided in simultaneously, so that composite of the present invention has excellent wearability, anti-flammability, heat resistance, higher gel content is obtained, so as to meet pressure-resistant demand of the material during high-temperature soldering.
Description
Technical field
The present invention relates to a kind of high withstand voltage cross-linking radiation environmental protection flame retardant composite rubber-plastic material and preparation method thereof.
Background technology
At present, with the emergence of various emerging industries such as Aero-Space, new energy power, photovoltaic building etc., to macromolecule
The standardisation requirements more and more higher of material, material update is increasingly frequent, and wherein ultrasonic bonding, high temperature hot melt etc. are also extensive
Apply in industry and manufacturing industry production.General-purpose plastics is typically using the relatively low polyolefine material of fusing point, and melting temperature is generally low
In 150 DEG C, and high-temperature soldering transient temperature is up to three or four hundred degree, and electric wire is due to high temperature and the shadow of external force in welding process
Ring and be easy to occur damaged or shrink, thus cause the failure of welding process with repeatedly.
Publication No. CN106380869A Chinese patent discloses a kind of 125 degree of cross-linking radiation new-energy automobile high-voltage lines
With elastomer cable material and preparation method thereof, by weight, the CABLE MATERIALS includes following components：Elastomer resin 10~
30%th, softening plasticizer 10~30%, processing modified resin 2~10%, resistance to oil-modified resin 5~15%, oil resistant improved elastic
Body 5~15%, compatilizer 2~10%, fire retardant 20~40%, fire retarding synergist 1~4%, antioxidant 0.5~2%, crosslinking are helped
Agent 0.5~2% and lubricant 0.5~2%.Though the CABLE MATERIALS employs the similar raw material in part, product overall performance and
Use occasion is inconsistent, it is impossible to meet the demand of high-temperature soldering.
The content of the invention
The technical problems to be solved by the invention are to overcome the deficiencies in the prior art there is provided a kind of high withstand voltage cross-linking radiation ring
Environment friendly flame-retardant composite rubber-plastic material and preparation method thereof.
To solve above technical problem, the present invention is adopted the following technical scheme that：
A kind of high withstand voltage cross-linking radiation environmental protection flame retardant composite rubber-plastic material, by weight, the raw material of the composite
Formula includes：
Wherein,
The high density polyethylene (HDPE) is less than or equal to 2g/10min high density polyethylene (HDPE) and melt index using melt index
The mixture of high density polyethylene (HDPE) more than or equal to 6g/10min, when the high density polyethylene (HDPE) for taking the two described melt index
During mixture, melt index is more than or equal to the ratio of 6g/10min high density polyethylene (HDPE) no more than total weight of the mixture
50%；
The elastomer resin include polyurethane elastomer and ethylene-propylene-diene monomer glue elastomer, the polyurethane elastomer and
The mass ratio of ethylene-propylene-diene monomer glue elastomer is 1：1~3.
The addition of the polyurethane elastomer causes product to have good wearability.
Further, high density polyethylene (HDPE) of the melt index less than or equal to 2g/10min and melt index are more than or equal to
The mass ratio of 6g/10min high density polyethylene (HDPE) is 1~2：0~1.
Further, ethylene contents are 55~75% in the ethylene-propylene-diene monomer glue elastomer.
Further, the BA contents of the EBA are that 15~30%, melt index is 5~25g/10min.The EBA's adds
Enter so that product has good heat resistance.
Further, the toughener is 1~3g/10min of melt index maleic anhydride grafted ethene-pungent dilute copolymer
With 0.5~2g/10min of melt index maleic anhydride grafted linear low density polyethylene in mass ratio 1:The mixing of 1~2 composition
Thing.
Further, the fire retardant is in surface treated magnesium hydroxide, aluminium hydroxide and melamine cyanurate
One or two kinds of mixtures, when in the fire retardant contain the melamine cyanurate when, the melamine cyanurate
Quality account for the 3~6% of the fire retardant gross mass.
Further, the antioxidant is a variety of of antioxidant 445, antioxidant 300, anti-oxidant DLTP and antioxidant 1010
Antioxidant 445 and antioxidant 1010 must be contained in mixture, the antioxidant.
Further, the lubricant is stearate, Tissuemat E, silicone oil in mass ratio 0.5~1：0.5~3：0.2
The mixture of~1 composition.
Further, the crosslinking agent is cumyl peroxide (DCP).
Further, the crosslinking sensitizer is trimethylol-propane trimethacrylate (TMPTMA), triallyl
One kind in isocyanuric acid ester (TAIC).
In the present invention, raw material described in whole can not have by commercially available and/or take known means to prepare
When being illustrated, the requirement of standard chemical products is satisfied by.
The another technical scheme that the present invention takes is：A kind of above-mentioned high withstand voltage cross-linking radiation environmental protection flame retardant composite rubber-plastic material
Preparation method, the preparation method comprises the following steps：
(1) high density polyethylene (HDPE), elastomer resin, EBA and crosslinking agent are added in homogenizer by formula and stirs equal
It is even, then through double-screw extruding pelletizing, wherein, extrusion temperature is 160 DEG C~200 DEG C；
(2) material grain and toughener, fire retardant, antioxidant, lubricant and the crosslinking sensitizer prepared step (1) adds high
Fast stirrer for mixing is uniform, then through banbury banburying, is then made successively through twin-screw mixer and single screw extrusion machine extrusion
Grain, is made the composite, wherein, mixing temperature is 160 DEG C~165 DEG C, single screw rod feed zone, melt zone and die head temperature
It is followed successively by 140 DEG C~160 DEG C, 165 DEG C~180 DEG C, 175 DEG C~190 DEG C.
Preferably, in step (1), two pieces 90 degree and 1 piece of left-hand thread group are needed in the twin-screw combination of the twin-screw
Close, screw slenderness ratio is 1：40.
Preferably, in step (2), the die head of the single screw rod uses 60 mesh, 100 mesh, the composite filter net of 40 mesh.
By the implementation of above technical scheme, the present invention has the following advantages that compared with prior art：
The present invention is formulated by improving, and is such as used as elastomer tree using polyurethane elastomer and ethylene-propylene-diene monomer glue elastomer
Fat, addition high density polyethylene (HDPE), EBA, while aiding in the materials such as addition toughener, fire retardant, antioxidant so that the present invention is compound
Material has a performances such as excellent wearability, anti-flammability, heat resistance, the degree of cross linking, higher gel content, and the composite can
Meet pressure-resistant demand of the material during high-temperature soldering.
Embodiment
The composite of the present invention not only has the excellent properties that each component is brought, and such as EBA makes product have well resistance to
Hot property, high density polyethylene (HDPE) makes product have good mobility, and elastic polyurethane makes product have good wearability, bullet
Property body resin make product that there is good mechanical performance etc., whole formula also has the advantage that formula globality is brought, such as dynamic
Sulfidation makes partial cross-linked component be dispersed in system, forms island structure, compared with ordinary irradiation is crosslinked, material
Higher crosslink density can be reached after material irradiation, structure is closer, so that material disclosure satisfy that during high-temperature soldering
Pressure-resistant demand.
The present invention is described in further detail with reference to specific embodiment.
The raw material used in following examples is commercially available standard industry product.
Embodiment 1
The present embodiment provides a kind of high withstand voltage cross-linking radiation environmental protection flame retardant composite rubber-plastic material, raw material and the consumption ginseng of use
1 is shown in Table, wherein：
High density polyethylene (HDPE)：By melt index for 0.9g/10min high density polyethylene (HDPE) (derive from grand celebration oil company,
The trade mark is 5000s) and melt index (derive from Dushanzi petro-chemical corporation, the trade mark is for 7.5g/10min high density polyethylene (HDPE)
6070) in mass ratio 1：0.5 composition.
Elastomer resin：By polyurethane elastomer (deriving from BASF AG) and ethylene-propylene-diene monomer glue elastomer (source
In the Dow Chemical Company) in mass ratio 1：1 composition, wherein, the ethylene contents in ethylene-propylene-diene monomer glue elastomer are 75%.
EBA：Select the EBA that BA contents 17%, melt index are 7g/10min.
Toughener：It is (public from Du Pont for 1g/10min maleic anhydride grafted ethene-pungent dilute copolymer by melt index
Department) and melt index for 0.5g/10min maleic anhydride grafted linear low density polyethylene (derive from E.I.Du Pont Company) by quality
Than 1：1 composition.
Fire retardant：Surface treated aluminium hydroxide (deriving from Albemarle Corporation, the trade mark is 104LEO) and cyanuric acid trimerization
The mixture of cyanamide, the quality of melamine cyanurate accounts for the 4% of fire retardant gross mass.
Antioxidant：By antioxidant 445, antioxidant 1010, antioxidant 300 in mass ratio 1：1：0.5 composition.
Lubricant：By magnesium stearate, Tissuemat E, silicone oil in mass ratio 0.5：1：0.3 composition.
Crosslinking agent：DCP.
Crosslinking sensitizer：TAIC.
The preparation method of composite comprises the following steps：
(1) high density polyethylene (HDPE), elastomer resin, EBA and crosslinking agent are added in homogenizer by formula and stirs equal
It is even, then through double-screw extruding pelletizing, wherein, extrusion temperature is 160 DEG C~200 DEG C；
(2) material grain and toughener, fire retardant, antioxidant, lubricant and the crosslinking sensitizer prepared step (1) adds high
Fast stirrer for mixing is uniform, then through banbury banburying, is then made successively through twin-screw mixer and single screw extrusion machine extrusion
Grain, is made composite, wherein, mixing temperature is 160 DEG C~165 DEG C, and single screw rod feed zone, melt zone and die head temperature are successively
For 140 DEG C~160 DEG C, 165 DEG C~180 DEG C, 175 DEG C~190 DEG C.
Embodiment 2
The present embodiment provides a kind of high withstand voltage cross-linking radiation environmental protection flame retardant composite rubber-plastic material, raw material and the consumption ginseng of use
Be shown in Table 1, it is following outside raw material it is same as Example 1.
High density polyethylene (HDPE)：The high density polyethylene (HDPE) and melt index for being 0.3g/10min by melt index are 20g/
10min high density polyethylene (HDPE) in mass ratio 1.5：0.5 composition.
Elastomer resin：By polyurethane elastomer and ethylene-propylene-diene monomer glue elastomer in mass ratio 3：4 compositions, wherein, three
Ethylene contents in first EP rubbers elastomer are 70%.
EBA：Select the EBA that BA contents 28%, melt index are 15g/10min.
Toughener：By maleic anhydride grafted ethene-pungent dilute copolymer and melt index of the melt index for 1.2g/10min
For 1.5g/10min maleic anhydride grafted linear low density polyethylene in mass ratio 1：1 composition.
Antioxidant：By antioxidant 445, antioxidant 1010, anti-oxidant DLTP in mass ratio 0.8：1：0.4 composition.
Crosslinking sensitizer：TMPTMA.
The preparation process be the same as Example 1 of composite.
Embodiment 3
The present embodiment provides a kind of high withstand voltage cross-linking radiation environmental protection flame retardant composite rubber-plastic material, raw material and the consumption ginseng of use
Be shown in Table 1, it is following outside raw material it is same as Example 1.
High density polyethylene (HDPE)：The high density polyethylene (HDPE) and melt index for being 2g/10min by melt index are 15g/10min
High density polyethylene (HDPE) in mass ratio 1：0.5 composition.
Elastomer resin：By polyurethane elastomer and ethylene-propylene-diene monomer glue elastomer in mass ratio 3：5 compositions, wherein, three
Ethylene contents in first EP rubbers elastomer are 65%.
The preparation process be the same as Example 1 of composite.
Embodiment 4
The present embodiment provides a kind of high withstand voltage cross-linking radiation environmental protection flame retardant composite rubber-plastic material, raw material and the consumption ginseng of use
Be shown in Table 1, it is following outside raw material it is same as Example 1.
EBA：Select the EBA that BA contents 28%, melt index are 20g/10min.
The preparation process be the same as Example 1 of composite.
Comparative example 1
This comparative example provides a kind of composite, the raw material and consumption of use referring to table 1, it is following outside raw material with reality
Apply example 1 identical.
High-density polyethylene resin is substituted by 2g/10min LLDPE.
Elastomer resin：Using ethylene propylene diene rubber one-component, the ethylene contents 65% wherein in ethylene propylene diene rubber.
The preparation process be the same as Example 1 of the composite of this contrast.
Comparative example 2
This comparative example provides a kind of composite, the raw material and consumption of use referring to table 1, it is following outside raw material with reality
Apply example 1 identical.
Without DCP.
EBA VA contents 28, melting means 7g/10min EVA is substituted.
The preparation process be the same as Example 1 of the composite of this contrast.
The raw material composition (number) of the embodiment 1~4 of table 1 and comparative example 1~2
| Raw material components | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Comparative example 1 | Comparative example 2 |
| Polyvinyl resin | 20 | 25 | 35 | 40 | 15 | 20 |
| Elastomer resin | 20 | 35 | 40 | 40 | 20 | 20 |
| EBA/EVA | 20 | 25 | 15 | 10 | 20 | 20 |
| Toughener | 20 | 15 | 10 | 10 | 8 | 20 |
| Fire retardant | 90 | 90 | 70 | 70 | 80 | 90 |
| Antioxidant | 1.5 | 1.5 | 1 | 1 | 1.5 | 1.5 |
| Lubricant | 1.5 | 1.5 | 1 | 1 | 1.5 | 1.5 |
| Crosslinking agent | 0.03 | 0.03 | 0.06 | 0.06 | 0.08 | 0.03 |
| Crosslinking sensitizer | 1.5 | 1.5 | 2 | 2 | 2 | 1.5 |
In table 1, for raw material components " polyvinyl resin ", embodiment 1~4 and comparative example 2 use high-density polyethylene
Alkene, comparative example 1 uses LLDPE；For raw material components " EBA/EVA ", embodiment 1~4 and comparative example 1
EBA is used, comparative example 2 uses EVA.
The composite of embodiment 1~4 and comparative example 1~2 is pressed into standard sample preparation, and properties are detected,
As a result referring to table 2.For ease of comparing, the desired value of the material company standard defined is also listed in table 2.
The performance of the composite of the embodiment 1~4 of table 2 and comparative example 1~2
The present invention is described in detail above, its object is to allow the personage for being familiar with this art to understand this
The content of invention is simultaneously carried out, and it is not intended to limit the scope of the present invention, and the invention is not restricted to above-mentioned implementation
Example, the equivalent change or modification that all Spirit Essences according to the present invention are made, should all cover in protection scope of the present invention.
Claims (10)
1. a kind of high withstand voltage cross-linking radiation environmental protection flame retardant composite rubber-plastic material, it is characterised in that by weight, the composite wood
The composition of raw materials of material includes：
15 ~ 45 parts of high density polyethylene (HDPE)；
25 ~ 50 parts of elastomer resin；
10 ~ 30 parts of EBA；
5 ~ 25 parts of toughener；
60 ~ 100 parts of fire retardant；
0.8 ~ 2 part of antioxidant；
1 ~ 2 part of lubricant；
0.03 ~ 0.1 part of crosslinking agent；
1 ~ 2.5 part of crosslinking sensitizer；
Wherein,
The high density polyethylene (HDPE) and melt index that the high density polyethylene (HDPE) is less than or equal to 2g/10min using melt index are more than
The mixture of high density polyethylene (HDPE) equal to 6g/10min, when the mixing for the high density polyethylene (HDPE) for taking the two described melt index
During thing, the ratio that melt index is more than or equal to 6g/10min high density polyethylene (HDPE) is no more than the 50% of total weight of the mixture；
The elastomer resin includes polyurethane elastomer and ethylene-propylene-diene monomer glue elastomer, the polyurethane elastomer and ternary
The mass ratio of EP rubbers elastomer is 1：1~3.
2. high withstand voltage cross-linking radiation environmental protection flame retardant composite rubber-plastic material according to claim 1, it is characterised in that：Described three
Ethylene contents are 55 ~ 75% in first EP rubbers elastomer.
3. high withstand voltage cross-linking radiation environmental protection flame retardant composite rubber-plastic material according to claim 1, it is characterised in that：It is described
EBA BA contents are that 15 ~ 30%, melt index is 5 ~ 25g/10min.
4. high withstand voltage cross-linking radiation environmental protection flame retardant composite rubber-plastic material according to claim 1, it is characterised in that：It is described to increase
The tough dose of maleic anhydride grafted ethene-pungent dilute copolymer and 0.5 ~ 2g/10min of melt index for 1 ~ 3g/10min of melt index
Maleic anhydride grafted linear low density polyethylene in mass ratio 1:The mixture of 1 ~ 2 composition.
5. high withstand voltage cross-linking radiation environmental protection flame retardant composite rubber-plastic material according to claim 1, it is characterised in that：The resistance
It is one or both of surface treated magnesium hydroxide, aluminium hydroxide and melamine cyanurate mixture to fire agent, works as institute
When stating in fire retardant containing the melamine cyanurate, the quality of the melamine cyanurate accounts for the fire retardant gross mass
3 ~ 6%.
6. high withstand voltage cross-linking radiation environmental protection flame retardant composite rubber-plastic material according to claim 1, it is characterised in that：It is described anti-
Oxygen agent is necessary in a variety of mixtures of antioxidant 445, antioxidant 300, anti-oxidant DLTP and antioxidant 1010, the antioxidant
Contain antioxidant 445 and antioxidant 1010.
7. high withstand voltage cross-linking radiation environmental protection flame retardant composite rubber-plastic material according to claim 1, it is characterised in that：The profit
Lubrication prescription is stearate, Tissuemat E, silicone oil in mass ratio 0.5 ~ 1：0.5~3：The mixture of 0.2 ~ 1 composition.
8. high withstand voltage cross-linking radiation environmental protection flame retardant composite rubber-plastic material according to claim 1, it is characterised in that：It is described to hand over
Connection agent is cumyl peroxide.
9. high withstand voltage cross-linking radiation environmental protection flame retardant composite rubber-plastic material according to claim 1, it is characterised in that：It is described to hand over
Connection sensitizer is one kind in trimethylol-propane trimethacrylate, Triallyl isocyanurate.
10. high withstand voltage cross-linking radiation environmental protection flame retardant composite rubber-plastic material described in any one of claim 1 ~ 9 claim
Preparation method, it is characterised in that the preparation method comprises the following steps：
（1）High density polyethylene (HDPE), elastomer resin, EBA and crosslinking agent are added by formula and stirred in homogenizer, so
By double-screw extruding pelletizing, twin-screw extrusion temperature is 160~200 DEG C；
（2）By step（1）Material grain and toughener, fire retardant, antioxidant, lubricant and the crosslinking sensitizer of preparation add high-speed stirring
Mix in machine and be well mixed, then through banbury banburying, then successively through twin-screw mixer and single screw extrusion machine extruding pelletization, system
The composite is obtained, wherein, mixing temperature is 160 DEG C ~ 165 DEG C, and single screw rod feed zone, melt zone and die head temperature are followed successively by
140℃~160℃、165℃~180℃、175℃~190℃。
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| CN110903589A (en) * | 2019-11-14 | 2020-03-24 | 苏州铂玛新材料有限公司 | High-voltage soft polyolefin wire material for new energy automobile and preparation method thereof |
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| CN112538200A (en) * | 2020-12-03 | 2021-03-23 | 江苏达胜高聚物股份有限公司 | Oil-resistant high-flame-retardant cable material and preparation method and application thereof |
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| CN114864163A (en) * | 2022-05-06 | 2022-08-05 | 湖北南远电缆科技有限公司 | High-temperature-resistant flame-retardant cable |
| CN115286864A (en) * | 2022-09-08 | 2022-11-04 | 苏州通优新材料科技有限公司 | Irradiation crosslinking polyolefin heat-shrinkable tube material and preparation method and application thereof |
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