CN106046232B - A kind of cross-linking ethylene-tetrafluoroethylene copolymer and its synthetic method - Google Patents
A kind of cross-linking ethylene-tetrafluoroethylene copolymer and its synthetic method Download PDFInfo
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- CN106046232B CN106046232B CN201610495122.1A CN201610495122A CN106046232B CN 106046232 B CN106046232 B CN 106046232B CN 201610495122 A CN201610495122 A CN 201610495122A CN 106046232 B CN106046232 B CN 106046232B
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- 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
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/26—Tetrafluoroethene
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Abstract
The present invention relates to a kind of cross-linking ethylene tetrafluoroethylene copolymers and preparation method thereof.The polymer is by tetrafluoroethene, ethylene, A monomers and B monomer are copolymerized, wherein A monomers are containing a double bond compound, B monomer is containing two double bond compounds, and the higher radiation resistance of ethylene tetrafluoroethylene copolymer, toughness, abrasivity, tensile strength and tearing strength can be assigned after appropriately crosslinked.Preparation method and crosslinkable copolymer compositions the present invention also provides cross-linking ethylene tetrafluoroethylene copolymer.The present invention reduces excessive oligomer, keeps the excellent performance of polymer by controlling polymerization technique.
Description
Technical field
The present invention relates to a kind of cross-linking ethylene-tetrafluoroethylene copolymer and its synthetic methods, belong to high molecular material
Technical field.
Background technology
Ethylene-tetrafluoroethylene copolymer (ETFE) has good chemical resistance, electrical property and resistance to ag(e)ing, pin-free
Film is suitable for the anticorrosions fields such as equipment liner, and the film or cable of good electric property are suitable for electronic computer, aviation boat
There is the membrane material of UV resistant and weatherability can be used for the fields such as the facility of open-air atmosphere and film for building in the fields such as it.For
For ETFE, the introducing of ethylene substantially increases radioresistance, and it is stronger severe to can be applied to the rays such as nuclear power station, space station
In environment, but crosslinking degree of its polymer itself is limited, and application effect in harsh environment will be restricted.
Japan AGC patent CN102089336A ethylene-tetrafluoroethylene copolymers provide a kind of melting tension it is high,
The good ethylene-tetrafluoroethylene copolymer of blow moldability, the modified monomer structure used for CH2=CH- (CF2) n-CH=CH2,
N is 4~8 integer, adds such modified monomer, can increase the flexibility of material to a certain extent, but due in polymer
More long flexible chain is introduced on molecular backbone or side group, thus the hardness of polymer and mechanical strength are difficult to improve.The U.S.
Du Pont patent CN104311763A is related to a kind of fluoropolymer elastomer, and the polymer mentioned is crosslinked for diacrylate esters
Fluoropolymer, structure CH2=CR ' COO- (CH2) n-R- (CH2) n-OOCR '=CH2, wherein R be included as tetrafluoroethene and
Olefin oligomer, molecular weight are the number-average molecular weight of 1000-25000 dalton, and R ' is H or-CH3, n 1-4.Such polymer
More oligomer is introduced, the processing performance of polymer, but thermal stability, chemical stabilization to polymer can be effectively improved
Property and mechanical performance etc. can have some impact on.Therefore, there is an urgent need for the stress cracking resistance that can improve ETFE and to poly-
The new technology that the mechanical performance of object adversely affects is closed, while the crosslinking points that should also effectively improve polymer reduce oligomer, keep away
Exempt from the related excellent performance of influence polymer.
The content of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of cross-linking ethylene-tetrafluoroethylene copolymer.
The present invention also provides a kind of preparation methods of cross-linking ethylene-tetrafluoroethylene copolymer composition.
Summary of the invention：
The cross-linking ethylene-tetrafluoroethylene copolymer of the present invention is with containing a double bond compound by tetrafluoroethene, ethylene
(A monomers) and two kinds of modified monomers containing two double bond compounds (B monomer) are copolymerized, can be assigned after appropriately crosslinked ethylene-
The higher radiation resistance of TFE copolymer, toughness, abrasivity, tensile strength and tearing strength.
Detailed description of the invention：
Technical scheme is as follows：
A kind of cross-linking ethylene-tetrafluoroethylene copolymer, the copolymer include：
The repetitive unit of repetitive unit and ethylene of about 80 moles of % to about 99.9 moles of % derived from tetrafluoroethene,
In, the molar ratio of tetrafluoroethene and ethylene is (0.5~1):(0.5~1)；With
Repetitive units of about 0.1 mole of % to about 20 moles of % derived from A monomers and B monomer：
A monomers are selected from perfluoroalkyl vinyl ether, hexafluoropropene, octafluoroisobutene, trifluoro propene, tetrafluoropropene, perfluoroalkyl
The monomer of ethylene, chlorotrifluoroethylene or vinylidene and their mixtures；
B monomer is selected from butadiene, isoprene, containing fluoroprene, fluorine-containing isoprene, fluorine-containing olefin(e) acid vinyl esters or complete
Fluorine olefin(e) acid vinyl esters and their mixture；
The molar ratio of the A monomers and B monomer is A/B=0.1~10.
Preferred according to the present invention, the ethylene-tetrafluoroethylene copolymer includes at least 45 moles of % and is derived from tetrafluoro second
The repetitive unit of alkene.
Preferred according to the present invention, the ethylene-tetrafluoroethylene copolymer includes at least 40 moles of % derived from ethylene
Repetitive unit.
A monomers of the present invention are containing a double bond compound, and primarily serving reduces ETFE crystallinity, improves its stress crack resistant
The effect of performance, preferably A monomer mole ratios are the 1-10% of polymer, and further preferred A monomer mole ratios are the 2- of polymer
6%.In the A monomers, preferred hexafluoropropene.
In B monomer described in the invention described above,
The fluorine-containing olefin(e) acid vinyl esters structure is：RfCR1=CR2-COOCH=CH2,
The fluorine-containing olefin(e) acid perfluorovinyl sulfide ester structure is：RfCR1=CR2-COOCF=CF2,
Wherein, Rf is alkyl, alkoxy, perfluoroalkyl or the perfluoro alkoxy alkyl of the saturation of 1 to 8 carbon atoms, R1,
R2 independently be expressed as H, F, Cl, CH3.It is preferred that Rf is CF3.
Further preferably, the fluorine-containing olefin(e) acid vinyl esters is CF3CH=CH-COOCH=CH2；The fluorine-containing alkene
Sour perfluoroethylene base ester is CF3CH=CH-COOCF=CF2.
Monomer B of the present invention is to contain two double bond compounds, in addition to a double bond with crosslinking is provided, branch
Presence can also effectively reduce the crystallinity of ethylene-tetrafluoroethylene copolymer (ETFE), enhance the stress cracking resistance of ETFE.
Monomer B content is excessively high, ETFE can be made to change to elastomer, the glass transition temperature of material can reduce, so as to reduce finished product
Temperature limit, if content is too low, role unobvious.Two kinds of the modified monomers A's and B involved in the present invention arrived
Molar ratio is A/B=0.1~10, preferred A/B=0.3~7, further preferred A/B=0.5~5.
The ethylene-tetrafluoroethylene copolymerization can be made by any one of existing suitable polymerisation process
Object, the suitable polymerisation process are included in radical polymerization initiator and trigger lower tetrafluoroethene, ethylene, A monomers and B monomer
Carry out free-radical polymerized, such as emulsion polymerization, suspension polymerization or solution polymerization.Wherein, emulsion polymerization
Since the degree of polymerization is high, at low cost, environmentally friendly, scheme is therefore preferred.It is usually fluorine-containing in the presence of appropriate surfactant
Surfactant such as perfluorooctanoic acid or other suitable surfactants close initiator using oil-soluble radical,
Implement emulsion polymerization in water.About 40 DEG C to 60 DEG C of polymeric reaction temperature be it is suitable, preferably 50 DEG C to 55 DEG C, and can
Using the pressure of about 1MPa to 5MPa.If desired, optionally copolymer can be adjusted using chain-transferring agent in the polymerization
Molecular weight.
Currently preferred, the radical polymerization initiator includes organic initiators, and the chain-transferring agent is selected from C1-C6
Alcohol, C1-C6 alkane or the fluorine-containing alkane of C1-C6.
Preferably, the organic initiators are selected from tert-Butyl peroxypivalate, peroxidating perfluorobutyrl compound
(CF3CF2CF2CO-OO-OCF2CF2CF3), special tert-butyl hydroperoxide isobutyric acid (PBIB) etc. selects organic initiators, polymerization
Object end group thermal stability is high, and reaction is gentler, easily-controllable.
Preferably, the chain-transferring agent is selected from methanol, ethyl alcohol or the tert-butyl alcohol.
The present invention also provides a kind of crosslinkable copolymer compositions, are total to including the above-mentioned ethylene-tetrafluoroethylene of the present invention
Polymers and at least one crosslinking agent.
There are three types of presently used cross-linked polymer routine crosslinking methods：It is peroxyde crosslinked, crosslinked with silicane and crosslinking with radiation.
Preferably, for easy-operating crosslinking method to add peroxide cross-linking agent in the polymer, the crosslinking agent is selected from peroxidating two
Isopropylbenzene (DCP), dibenzoyl peroxide (BPO), di-tert-butyl peroxide (DTBP), di-isopropylbenzene hydroperoxide (DBHP)
Deng.The content of crosslinking agent is to be generally the 0.2-4% of polymer, preferably 2% or so；
The performance characterization test of cross-linked samples：A certain amount of polymer, peroxide cross-linking agent are inserted Brabender to turn
In square rheometer mixer, (280 DEG C or so) mixing 5min or so under the conditions of the relative low temperature after material melts are chosen, using flat
Cross-linked polymer plate is made in plate vulcanizer (300 DEG C or so), then carries out correlated performance characterization to it.
The technical characterstic and excellent results of the present invention：
1st, ethylene-tetrafluoroethylene copolymer of the present invention contains two kinds of double bond modified monomer structures, wherein, there are one A monomers contain
Double bond can reduce the crystallinity of polymer, improve its stress cracking resistance, and reduce melt viscosity, improve processing performance；Together
When, the phenomenon that causing to cause mechanical performance and reduce the adhesion strength of substrate in order to avoid the crystallinity for reducing copolymer merely,
The present invention is also containing there are two double bond compound B monomers so that there is more double bond in polymer, it is appropriately crosslinked significantly to carry
Radiation resistance, toughness, abrasivity, tensile strength and the tearing strength of high finished product.
2nd, the present invention has chosen two class monomers and performance improvement is carried out to ETFE, and a kind of A monomers contain the compound of a double bond,
Because it is rigid short-chain branch, so as to generate apparent adverse effect to the mechanicalness of polymer, and another kind of B monomer be containing
The compound of two double bonds can effectively improve the crosslinking points of polymer, while can be reduced excessive by controlling polymerization technique
Oligomer avoids influencing the related excellent performance of polymer.The effect that described two kinds of modified monomers of A, B emphasize particularly on different fields, and energy
Have complementary advantages, may be such that polymer has both the various excellent performances that can meet application demand.
Specific embodiment
The present invention is specifically described by following embodiment, but the invention is not limited in these embodiments.
The composition ratio of each monomeric unit passes through F in polymer prepared by embodiment19- NMR and IR analysis and measurements.
Melt index is measured by fusion index instrument, and testing standard is ASTM-D1238 (297 DEG C of * 49N).
Add in polymer volume than 2% content cumyl peroxide, utilize brabender torque rheometer mixings
After machine blending, standard batten is prepared using vulcanizing press and dumbbell shape cutter, carrying out fracture using 638 standards of ASTM D stretches
Long rate, the measure of tensile strength.
Light transmittance tests polymer using GBT2410-2008 methods.
Tear-resistant strength test, under the conditions of 300 DEG C, squeeze polymer forms 100 μ m-thick films, according to GB/
T16578.9-2009 methods are tested using Ai Laimenduofu type testing machines.
Embodiment 1
3L deionized waters are squeezed into 5L stainless steel autoclaves；210g trifluorotrichloroethanes (CFC-113)；20g matter
Measure the perfluoro ammonium caprylate solution of fraction 30%；System is vacuumized, until oxygen content is in below 10ppm.Add in 25g parts fluoro
Butenoic acid vinyl esters CF3CH=CH-COOCH=CH2 and 5.1g methanol heats up under stirring state, keeps temperature stabilization 50
DEG C, molar ratio 25 is added in into system with compressor:75:20 Yi Xi Si Fuyixi hexafluoropropenes mix gas, to maintain
Hexafluoropropene has certain solubility in water, until pressure is 1.5MPa, improves mixing speed to 350 revs/min, passes through
The CFC-113 solution that metering device is persistently pumped into 30mL tert-Butyl peroxypivalates containing 0.55g into system triggers polymerization anti-
Should carry out, be continually fed into ethylene tetrafluoroethene hexafluoropropene molar ratio be 48：43：The mixing gas dimension of 5 (polymer proportionings)
Hold pressure makes reaction constantly carry out in 1.2MPa, when the gaseous mixture scale of construction of input reaches 252g or so, stops reaction, will be in kettle
Temperature is down to room temperature, recycles unreacted mixed gas in kettle, and opens baiting valve and release material.Demulsification, washing and drying
White polymer powder 235g is obtained afterwards.Each monomer unit content of test polymer, melt index, elongation at break, stretching are strong
Degree, light transmittance and tear-resistant intensity, these data are listed in the table below.
Embodiment 2~4
As described in Example 1, except that different amounts of CF3CH=CH-COOCH=CH2 is added in, to resulting polymers
It is analyzed, related test result is listed in table 1.
Embodiment 5~7
As described in Example 1, except that fixed CF3CH=CH-COOCH=CH2 additions, change hexafluoropropene
Additional proportion analyzes resulting polymers, and Measurement results are listed in table 1.
1 resulting polymers content analysis of table and correlated performance characterize data
Embodiment 8~11
Using different types of modified monomer A and B, embodiment 1 is repeated, resulting polymers are analyzed, test analysis
The results are shown in tables 2.
2 resulting polymers correlated performance characterize data of table
Comparative example 1：Only use modified monomer A
As described in Example 1, the difference is that not adding CF3CH=CH-COOCH=CH2.
Comparative example 2：Only use modified monomer B
As described in Example 1, the difference is that without using hexafluoropropene monomer.
The performance test experimental result of comparative example 1-2 resulting polymers is as shown in table 3.
3 comparative example resulting polymers correlated performance characterize data of table
Claims (10)
1. a kind of cross-linking ethylene-tetrafluoroethylene copolymer, the copolymer include：
The repetitive unit of repetitive unit and ethylene of 80 moles of % to 99.9 moles of % derived from tetrafluoroethene, wherein, tetrafluoro second
The molar ratio of alkene and ethylene is 0.5 ~ 1:0.5~1；With
Repetitive units of 0.1 mole of % to 20 moles of % derived from A monomers and B monomer：
A monomers are selected from perfluoroalkyl vinyl ether, hexafluoropropene, octafluoroisobutene, trifluoro propene, tetrafluoropropene, perfluoroalkyl second
The monomer of alkene, chlorotrifluoroethylene or vinylidene and their mixtures；
B monomer is selected from butadiene, isoprene, containing fluoroprene, fluorine-containing isoprene, fluorine-containing olefin(e) acid vinyl esters or perfluor alkene
Sour vinyl esters and their mixture；Wherein, the fluorine-containing olefin(e) acid vinyl esters structure is：RfCR1=CR2-COOCH
=CH2, the perfluor olefin(e) acid vinyl esters structure are：RfCR1=CR2-COOCF=CF2,
Wherein, Rf is alkyl, alkoxy, perfluoroalkyl or the perfluoro alkoxy alkyl of the saturation of 1 to 8 carbon atoms, and R1, R2 divide
Not independent is expressed as H, F, Cl, CH3；
The molar ratio of the A monomers and B monomer is A/B=0.1~10.
2. cross-linking ethylene-tetrafluoroethylene copolymer as described in claim 1, it is characterised in that the ethylene-tetrafluoroethylene
Copolymer includes the repetitive unit that at least 45 moles of % are derived from tetrafluoroethene.
3. cross-linking ethylene-tetrafluoroethylene copolymer as described in claim 1, it is characterised in that the ethylene-tetrafluoroethylene
Copolymer includes the repetitive unit of at least 40 moles % derived from ethylene.
4. cross-linking ethylene-tetrafluoroethylene copolymer as described in claim 1, which is characterized in that A monomer mole ratios are polymerization
The 2-6% of object.
5. cross-linking ethylene-tetrafluoroethylene copolymer as claimed in claim 1 or 2, which is characterized in that in the B monomer,
The fluorine-containing olefin(e) acid vinyl esters is CF3CH=CH-COOCH=CH2；The fluorine-containing olefin(e) acid perfluoroethylene base ester is
CF3CH=CH-COOCF=CF2。
6. cross-linking ethylene-tetrafluoroethylene copolymer as described in claim 1, which is characterized in that the A monomers and B monomer
Molar ratio be A/B=0.3~7.
7. cross-linking ethylene-tetrafluoroethylene copolymer as described in claim 1, which is characterized in that the A monomers and B monomer
Molar ratio be A/B=0.5~5.
8. a kind of preparation method of the cross-linking ethylene-tetrafluoroethylene copolymer of claim 1-7 any one of them, in free radical
In the presence of polymerization initiator, tetrafluoroethene, ethylene, A monomers and B monomer carry out free-radical polymerized；It is described free-radical polymerized to be selected from
Polymerisation in solution, suspension polymerisation or emulsion polymerization.
9. the preparation method of cross-linking ethylene-tetrafluoroethylene copolymer as claimed in claim 8, it is characterised in that radical polymerization
It closes initiator and is selected from tert-Butyl peroxypivalate or peroxidating perfluorobutyrl compound.
10. a kind of crosslinkable copolymer compositions, including the cross-linking ethylene of claim 1-7 any one of them-tetrafluoro second
Alkene copolymer and at least one crosslinking agent；The crosslinking agent is selected from cumyl peroxide, dibenzoyl peroxide, two tertiary fourths
Base peroxide or di-isopropylbenzene hydroperoxide.
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| CN101821301B (en) * | 2007-10-12 | 2012-06-27 | 3M创新有限公司 | Process for manufacturing clean fluoropolymers |
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| CN101001894A (en) * | 2004-08-04 | 2007-07-18 | 旭硝子株式会社 | Elastic fluorocopolymer, its composition and crosslinked rubber |
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