CN110330594A - A kind of method that polyethylene crosslinking is modified - Google Patents
A kind of method that polyethylene crosslinking is modified Download PDFInfo
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- CN110330594A CN110330594A CN201910597420.5A CN201910597420A CN110330594A CN 110330594 A CN110330594 A CN 110330594A CN 201910597420 A CN201910597420 A CN 201910597420A CN 110330594 A CN110330594 A CN 110330594A
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- crosslinking
- protective embankment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
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Abstract
The invention belongs to technical field of material modification, disclose a kind of method that polyethylene crosslinking is modified, the silane cross-linking method that the modified method of polyethylene crosslinking is PE, it is basic resin that silicon protective embankment, which is crosslinked PE with PE, it is bridged bond material by silicon protective embankment, chemical covalent bonds are formed to replace original Van der Waals force in polymer macromolecule interchain, so that molecule is constituted 3 D stereo network, the preparation that silicon protective embankment is crosslinked PE includes grafting and two stages of crosslinking.The method that the present invention uses crosslinked with silicane, without high equipment investment, it can get higher extruded velocity, and it can be reduced the waste material of start-up phase generation, the ageing-resistant ability of its polyethylene being crosslinked is better than other preparation methods, and technically simple and stable crosslinked with silicane mode can be applied to large range of compound processing.
Description
Technical field
The invention belongs to a kind of modified methods of technical field of material modification more particularly to polyethylene crosslinking.
Background technique
Currently, the prior art commonly used in the trade is such that modern plastics have very excellent physical property, it is only limited by
The influence of its relatively poor heat resistance, service life is still limited in many application fields, PE due to its design feature,
It cannot bear higher using temperature, mechanical strength is lower in addition, limits it in the application in many fields.In order to improve PE's
Heat-resisting and mechanical property, effective method be it is carried out it is cross-linking modified.
For crosslinked polyethylene, exactly because it makes it have more with unique three-dimensional netted molecular structure
Outstanding performance.Crosslinked polyethylene because its excellent machining property makes it be widely used in tubing process industry, and by
Step replaces the non-crosslinked plastic pipes such as polypropylene, polyvinyl chloride and various thermoplastic polyethylenes.Requiring higher application
In field, such as auto manufacturing, cross-linking polyethylene materials can be used to the higher engineering plastics of alternative cost.Crosslinked polyethylene
For foam in the application of automotive field, main application includes cresting in automobile, and luggage case, lateral coaming plate, heat insulating mattress, protects in door ground cushion
Plate, water-proof curtain, sunshading board, Waxing disc, air-conditioning system etc..Have much for the cross-linked modification method of polyethylene at present, but
It generally requires to put into high equipment when being modified, Technical comparing is complicated, generates more waste material, causes biggish economic damage
It loses.
In conclusion problem of the existing technology is: it is high to generally require investment when being modified to polyethylene at present
High equipment, Technical comparing is complicated, generates more waste material, causes biggish economic loss.
Summary of the invention
In view of the problems of the existing technology, a kind of method modified the present invention provides polyethylene crosslinking.
The invention is realized in this way a kind of method that polyethylene crosslinking is modified are as follows: the silane cross-linking method of PE, the crosslinking of silicon protective embankment
PE is basic resin with PE, is bridged bond material by silicon protective embankment, and it is original to replace to form chemical covalent bonds in polymer macromolecule interchain
Van der Waals force, make molecule constitute 3 D stereo network, silicon protective embankment be crosslinked PE preparation include be grafted and crosslinking two stages.
Grafting stage: peroxide initiator is decomposed thermally to form primary group of free radicals, and primary group of free radicals captures PE macromolecular
H atom on chain forms PE macromolecular radical, the free radical and vinyl trialkyl oxysilane CH2=CH-Si(OR)3In
Vinyl carries out addition reaction, forms PE and is grafted silicon protective embankment active macromolecules, the active macromolecules are by capturing the reality of the H atom in PE
Existing chain tra nsfer obtains PE grafting silicon protective embankment product i.e. grafted material A；
Cross-linking stage: PE grafted silane product hydrolyzes under the action of organic tin catalyst generates silanol, and silanol passes through
Dehydration or dealcoholysis form PE silicon protective embankment cross-linking products.
Further, the base resin is the homopolymer and copolymer of the alkene after being dried.
Further, the initiator is DCP, and the dosage of DCP is 0.05-0.5 parts.
Further, the crosslinking agent uses vinyl unsaturated silane, and dosage of crosslinking agent is between 0.5-4 parts.
Further, the antioxidant is antioxidant 330,168,1010, RD and other aromatic amine stabilizers, be can also be used
Compound antioxidant, antioxidant content are not more than 1 part.
Further, the crosslinking catalyst is dibutyl tin dilaurate ester, and dosage isPart.
Further, compound polymerization inhibitor is added in the polymerization inhibitor in grafting process.
In conclusion advantages of the present invention and good effect are as follows: the method that the present invention uses crosslinked with silicane, without high
Equipment investment can get higher extruded velocity, and can be reduced the waste material of start-up phase generation, the polyethylene of crosslinking it is resistance to old
Change ability is better than other preparation methods, and technically simple and stable crosslinked with silicane mode can be applied to large range of compound
Object processing.
Detailed description of the invention
Fig. 1 is the preparation method flow chart of silicon protective embankment crosslinking PE provided in an embodiment of the present invention.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
Application principle of the invention is described in detail with reference to the accompanying drawing.
The modified method of polyethylene crosslinking provided in an embodiment of the present invention are as follows: the silane cross-linking method of PE, silicon protective embankment be crosslinked PE with
PE is basic resin, is bridged bond material by silicon protective embankment, forms chemical covalent bonds in polymer macromolecule interchain to replace original model
De Huali makes molecule constitute 3 D stereo network, and the preparation that silicon protective embankment is crosslinked PE includes to be grafted and be crosslinked two stages (such as Fig. 1 institute
Show).
S101: grafting stage: peroxide initiator is decomposed thermally to form primary group of free radicals, and it is big that primary group of free radicals captures PE
H atom on strand forms PE macromolecular radical, the free radical and vinyl trialkyl oxysilane CH2=CH-Si(OR)3
In vinyl carry out addition reaction, formed PE be grafted silicon protective embankment active macromolecules, the active macromolecules by capture the H in PE original
Son realizes that chain tra nsfer obtains PE grafting silicon protective embankment product i.e. grafted material A.
S102: cross-linking stage: PE grafted silane product hydrolyzes under the action of organic tin catalyst generates silanol, silanol
PE silicon protective embankment cross-linking products are formed by dehydration or dealcoholysis.
Base resin provided in an embodiment of the present invention is the homopolymer and copolymer of the alkene after being dried.
Initiator provided in an embodiment of the present invention is DCP, and the dosage of DCP is 0.05-0.5 parts.
Crosslinking agent provided in an embodiment of the present invention uses vinyl unsaturated silane, and dosage of crosslinking agent is between 0.5-4 parts.
Antioxidant provided in an embodiment of the present invention is antioxidant 330,168,1010, RD and other aromatic amine stabilizers,
Compound antioxidant can also be used, antioxidant content is not more than 1 part.
Crosslinking catalyst provided in an embodiment of the present invention is dibutyl tin dilaurate ester, and dosage is 0.02-~0.15 part.
Compound polymerization inhibitor is added in polymerization inhibitor provided in an embodiment of the present invention in grafting process.
The invention will be further described combined with specific embodiments below.
Embodiment 1
Influence silane grafting and crosslinking PE because being known as:
Base resin: the homopolymer and copolymer of alkene all can be by unsaturated silicon protective embankment graft crosslinkings.Different PE are because of its structure
The degree of difference, the melt flow rate (MFR) decline of grafting front and back is different.In specific production, individually a kind of resin is difficult to meet
Comprehensive performance requirement generallys use the method for several resin alloys to adjust the fundamental characteristics of resin, to wish to reach expected
PE crosslinked products.In addition, Silane Grafted has strict demand to the water content of polymer.Silicon protective embankment, which encounters the moisture in polymer, to be sent out
Unboiled water solution simultaneously generates precrosslink, will seriously affect the quality of product.So polymer will be dried before use.
Initiator: the common initiator of silane grafting and crosslinking PE is DCP, and decomposition temperature and half-life period can meet PE tree
Rouge and organic silicon monomer melting graft reaction condition.In the case that other conditions are certain, with the increase of DCP dosage, PE is connect
Branch efficiency is varied.The dosage of DCP is generally 0.05-0.5 parts.
Crosslinking agent: crosslinking agent generally uses vinyl unsaturation silicon protective embankment as crosslinking agent, including vinyl trimethoxy silicon
Protective embankment and vinyltriethoxysilane.Dosage of crosslinking agent is generally between 0.5-4 parts.
Antioxidant: if antioxidant is added before grafting, silicon protective embankment graft reaction can be generated and is significantly affected, especially freely
The antioxidant of the capturing agent type of base inhibits graft reaction because they can capture PE free radical.So antioxygen in grafting process
The addition of agent is prudent, should select suitable antioxidant.Common antioxidant has antioxidant 330,168,1010, RD and other virtues
Fragrant amines stabilizer, can also be used compound antioxidant.General antioxidant content is not more than 1 part.
Crosslinking catalyst: the most common catalyst of crosslinking catalyst is dibutyl tin dilaurate ester (DBDTL), and dosage isPart.Crosslinking catalyst is added generally there are two types of form, one is directly plus people to PE expect in or with masterbatch shape
Formula is added；Another kind is to coat one layer of catalyst in the outer surface of product, and first method uses more.
Polymerization inhibitor: in the grafting of silicon protective embankment and cross-linking process many side reactions inevitably occur for polymerization inhibitor, these are secondary anti-
The processing and storage of reply crosslinking PE is unfavorable, so the generation of this kind of reaction should be reduced to the greatest extent.In order to reduce these side reactions, adopt
The approach taken is that compound polymerization inhibitor is added in grafting process.
Embodiment 2
Influence silane grafting and crosslinking PE because being known as:
(1) factor of PE silane grafting process is influenced
The main process factor for influencing PE Silane Grafted is extrusion temperature and extruded velocity.The speed of graft reaction mainly takes
Certainly in the decomposition rate of graft initiator, and the decomposition rate of graft initiator is strongly dependent on extrusion temperature.With temperature
Degree increases, and the half-life period of initiator reduces, and improves extrusion temperature and is conducive to improve graft reaction speed.But extrusion temperature is excessively high,
Silane monomer volatilization, reduces grafting rate.PE Silane Grafted reaction temperature general control is between 190-210 DEG C.Extruder turns
Quick decision earnest material residence time (reaction time) and mixed effect in an extruder.Residence time is too short, and peroxide decomposes
Not exclusively, reduce grafting rate, residual peroxide will have a direct impact on grafted material long-time stability and product mouldability and
Appearance.Residence time is too long, and the viscosity of extruded material increases and influences processing performance.In general, PE is required to squeeze in technique
The mean residence time in machine should control 5-10 times in decomposition of initiator half-life period out.Rate of feeding not only has the residence time
It is certain to influence, and rate of feeding is different, and the filling extent of screw channel is different, thus influences screw rod and make to the mixing of material and shearing
With.Feeding is too fast, and the material discharging of extrusion is uneven, rough, is in Bamboo-shaped, processing performance is poor.Feeding is too slow, economical
Property is uneconomical.
(2) two kinds of techniques of silicon protective embankment graft crosslinking PE preparation:
One-step method: originate from M0n0sil technology, it is disposably to enter raw material by special delicate metering system
In the extruder specially designed, a step completes grafting and molding technique.
Two-step method: from the Sioplase technology of Dow Corning Corporation.The first step is that Silane Grafted PE pellet and catalysis are female
Prepared by the mixing extrusion of material, second step is grafting PE pellet and catalysis masterbatch and PE-extrusion moldings, and product is in hot water or low
It is crosslinked under pressure steam.
Other cross-linking methods are further described combined with specific embodiments below.
(1) high-energy radiation cross-linking method
Radiation cross-linking process (PE-Xc) is to irradiate molded product by β ray or gamma-rays, makes to be formed between polyethylene molecule
C-C cross-bond.Resulting product is pure, and electric property is superior, but radiation generating device is expensive, and radiation penetration capacity is limited, no
Suitable for making thick-walled product or complicated product, are chiefly used in the production of CABLE MATERIALS, heat-shrinkable tube and specialty films.
PE is a kind of typical radiation-cross-linkable polymer.How Qu accelerates crosslinking with radiation, side reaction, reduction is inhibited to reach
Irradiation dose (the sensitized radiation problem of namely PE) when required gel content has become the emphasis of current research.
The conventional method of PE sensitized radiation problem is sensitizer and sensitizer to be added in PE (also someone is by sensitizer and quick
Agent is referred to as sensitizer or sensitizer), or change irradiation atmosphere (such as in acetylene, tetrafluoroethene atmosphere).
The advantage and disadvantage of PE high-energy radiation cross-linking method:
Advantage: good processing stability；Manufactured goods are pure.
Disadvantage: expensive additional processing equipment；More demanding working environment；It is only applicable to thin-wall product；It is difficult to complete
The crosslinking of coil pipe.
(2) peroxide crosslinking of PE
The advantages that peroxide crosslinking is adaptable strong, crosslinked products performance is good, thus obtain industrial application.
Peroxide crosslinking and crosslinking with radiation the difference is that:
Its cross-linking process must be crosslinking dose, i.e., peroxide exists；
Cross-linking reaction must carry out at a certain temperature.
When crosslinking agent is simple peroxide, reaction process is as follows: peroxide is thermally decomposed to generate free radical, from
By base attack PE macromolecular chain, capture the hydrogen atom on strand, generates PE macromolecular chain free radical；PE macromolecular chain free radical
It with highly reactive, when two PE strand free radicals meet, just be combined with each other, forms the chemical bond between macromolecular chain
And it is crosslinked.
Crosslinking agent used in peroxide crosslinking is organic peroxide, and common kind mainly has DCP, BPO etc..It is used
When oxide is crosslinked PE, extrusion temperature must keep very low, once extrusion temperature is higher than the decomposition temperature of peroxide, early stage
Crosslinking, which may cause, there is coking, and the quality for influencing product even damages equipment, which strictly limits cross-linking PE
Extruded velocity to there is dedicated extruder and high pressure to be continuously crosslinked pipeline, which limits the skills and in extruded product
Art is in, the application of small enterprise.
The advantage and disadvantage of the peroxide crosslinking of PE
Advantage: the higher degree of cross linking；It is preferable flexible.
Disadvantage:, Yao Gaowen more demanding to production equipment easily causes polyethylene molecule chain rupture, and speed of production is slower, efficiency
It is lower.
(3) the ultraviolet lighting crosslinking of PE
Ultraviolet light can also be such that PE crosslinks, and ultraviolet light cross-linking is changed into after absorbing UV energy by photoinitiator
Then excitation state takes hydrogen by force on PE chain and generates free radicals and cause PE crosslinking.
The breakthrough of the ultraviolet lighting crosslinking of PE
1. high power high-pressure sodium lamp is selected to replace low pressure mercury lamp, light intensity is not only increased, and make its launch wavelength range
It is suitable for the absorption of photoinitiator used；
2. being crosslinked using molten state, ultraviolet light is on the one hand set to penetrate readily through PE thickness sample, on the other hand due to temperature
Raising increase the motility of macromolecular radical to be crosslinked, to accelerate reaction speed, improve the uniform of crosslinking
Property；
3. causing cross-linking process initially using the efficient initiation system of multi-group crosslink agent and photoinitiator cooperation
Completed in short time in stage, not only increase crosslinking velocity of initiation, and by the depth of crosslinking by 0.3mm be increased to 3mm with
On.
The advantages of ultraviolet lighting crosslinking of PE
Ultraviolet light cross-linking technology has the advantages that its uniqueness, it is similar to high energy electron beams method in technical principle, but
It is that it uses the ultraviolet light of low energy as radiation source, equipment is easy to get, and investment cost is low, and easy to operate, protection is easy.Therefore, PE
Ultraviolet light cross-linking technology be increasingly valued by people, especially in development crosslinking electric wire and various low-voltage crosslinked cable sides
Face has the biggish market competitiveness, hews out a road Tiao Xin for PE crosslinking technological.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (7)
1. a kind of modified method of polyethylene crosslinking, which is characterized in that the modified method of the polyethylene crosslinking uses the silicon of PE
Alkane cross-linking method, it is basic resin that silicon protective embankment, which is crosslinked PE with PE, is bridged bond material by silicon protective embankment, forms chemistry in polymer macromolecule interchain
Covalent bond makes molecule constitute 3 D stereo network to replace original Van der Waals force；It is carried out in the preparation of silicon protective embankment crosslinking PE:
Grafting stage: peroxide initiator is decomposed thermally to form primary group of free radicals, and primary group of free radicals is captured on PE macromolecular chain
H atom form PE macromolecular radical, the free radical and vinyl trialkyl oxysilane CH2=CH-Si(OR)3In ethylene
Base carries out addition reaction, forms PE and is grafted silicon protective embankment active macromolecules, which realizes chain by capturing the H atom in PE
Transfer obtains PE grafting silicon protective embankment product i.e. grafted material A；
Cross-linking stage: PE grafted silane product hydrolyzes under the action of organic tin catalyst generates silanol, and silanol passes through dehydration
Or dealcoholysis forms PE silicon protective embankment cross-linking products.
2. the modified method of polyethylene crosslinking as described in claim 1, which is characterized in that the base resin is to be dried
The homopolymer and copolymer of alkene later.
3. the modified method of polyethylene crosslinking as described in claim 1, which is characterized in that the initiator is DCP, DCP's
Dosage is 0.05-0.5 parts.
4. the modified method of polyethylene crosslinking as described in claim 1, which is characterized in that the crosslinking agent uses vinyl not
It is saturated silane, dosage of crosslinking agent is 0.5-4 parts.
5. the modified method of polyethylene crosslinking as described in claim 1, which is characterized in that the antioxidant be antioxidant 330,
168,1010, RD and other aromatic amine stabilizers, can also be used compound antioxidant, and antioxidant content is not more than 1 part.
6. the modified method of polyethylene crosslinking as described in claim 1, which is characterized in that the crosslinking catalyst is two laurels
Sour two fourth tin esters, dosage are 0.02-~0.15 part.
7. the modified method of polyethylene crosslinking as described in claim 1, which is characterized in that the polymerization inhibitor is in grafting process
Compound polymerization inhibitor is added.
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| CN112208114A (en) * | 2020-09-14 | 2021-01-12 | 与时高分子科技(湖北)有限公司 | Preparation method of high-density polyethylene cross membrane |
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| CN114133654A (en) * | 2021-12-17 | 2022-03-04 | 广州爱奇实业有限公司 | Polyethylene composition, preparation method and application thereof |
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Application publication date: 20191015 |