• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    A crosslinking composition comprising a blend of at least two polyallylic esters of polycarboxylic acids, one of said esters being a diallylic ester of an alkyl, cycloalkyl, mixed alkyl-cycloalkyl or aralkyl dicarboxylic acid, the other of said esters being a polyallylic ester of an aromatic or heteroaromatic polycarboxylic acid or triallyl ester of isocyanuric acid. The crosslinking compositions are particularly useful as crosslinking coreactants for high temperature processing fluorocarbon polymers. The products resulting from the mixing of fluorocarbon polymers and blends of diallyl esters with triallyl or tetraallyl esters are particularly useful as coatings for wire products.
    公开号:SU902671A3
    申请号:SU742071900
    申请日:1974-10-01
    公开日:1982-01-30
    发明作者:Дж.Аронофф Элиху；Сайн Дэми Кьюал
    申请人:Интернэшнл Стандарт Электрик Корпорейшн (Фирма)；
    IPC主号:
    专利说明:

    one
    The invention relates to crosslinking compositions based on fluorocarbon polymers with the addition of polyaryl esters of polycarboxylic acids.
    Polymer compositions 5 based on fluorocarbon polymers and diallyl ethers of dicarboxylic acids 1 are known.
    The diallyl esters of dicarboxylic acids possess an advantageous combination of solutions that allow them to be used in plasticizing and cross-linking. Dimensional compositions, in particular, for high-temperature processing of fluorocarbon compounds. Formallyl 15 ethers have a plasticizing effect on fluorocarbon polymers during their processing under high temperature conditions, and also allow to obtain crosslinked polymers with good chemical, electrical and mechanical properties.
    However, fluorocarbon polymers crosslinked by di-methyl esters of dicarboxylic acids have low resistance.
    to deformation at high temperatures.
    The closest in technical essence is a composition based on a fluorocarbon polymer and, as a crosslinking agent, a mixture of two
    -about
    polyallyl esters of polycarboxylic acid, one of which is a dicarboxylic acid diallyl ester and the other is a carboxylic ester having three carboxyl groups 2.
    The disadvantage of these compositions is that they also have insufficient resistance to deformation and elasticity.
    The purpose of the invention is to increase the elasticity and resistance to deformation.
    To achieve this goal, a polymer composition based on a fluorocarbon polymer containing polyallyl ester of polycarboxylic acidmars who are on-campus, have been selected as a mixture of ethylene with tetrafluoroephene or 3 chlorotfluoroethylene, and as a polycarbonic acid of polycarboxylic acids, it is a triple mixture of triple fluoroethylenes and polychloric acid; trimellitic, trimesic n isocyanuric acid, with diallyl ester of brassilic or phenylindic acid carboxylic acid at and B refer to the triallyl ether diallilov mu 1: 4-4: 1, with the following component-weight.%: ethylene tetrafluoroethylene copolymer or mixture hlortriftorztilenom92-97 trigshlilovogo polycarboxylic acid ester and diallyl ether or brassidovoy fe shlindandikarbonovoy acid in a ratio of 1: 4-4: 1 3-8 The mixtures of polyallyl ethers have very good crosslinkable properties in high temperature processing. The proposed diallyl ethers have a very good ossing pattern, its action during high-temperature processing processes and, in combination with triallyl ethers, provide excellent mechanical properties at high temperatures and resistance to Diformations and crosslink polymers. Example 1. This and the following examples illustrate a significant and unexpected increase in crosslinking efficiency achieved through the use of mixtures of diallyl and triallyl ethers, compared with the use of individual esters, the polymer composition (hereinafter, Composition A) is obtained by mixing an ethylene copolymer with tetrafluoroethylene with 3 wt.% triallyl trimellitate. The second polymer composition (hereinafter - soybean B) is also obtained by mixing a copolymer of ethylene with tetrafluoroethylene with 3 wt.% Diallylbrasylate. It should be noted that formulations A and B were obtained as control samples. The third and fourth polymeric composition (hereinafter referred to as compounds C and D) are obtained in a similar way by mixing a copolymer of ethylene with tetrafluoroethylene with a mixture of triallyl trimellitate and diallylbrasse. Composition C contains 1.5 wt.% Trimellitate and 1.5 wt. % brassilata, and the composition of D - 1.0 wt.% trimellitate and 2.0 wt.% brassilata. Magnesium oxide in the amount of 1 wt.% Is added to each of these compositions. Each of the mixes is then molded under pressure with five minutes preheating followed by four minutes of direct compression at 271.2-276.7 C under a pressure of about 700 atm. . The irradiation of the product of direct molding is carried out preferably with a dose of 10 Mrad in a 1.5 MeV radiation electron accelerator to obtain a cross-linked polymer composition having the following mechanical properties (Table 1) at elevated temperature () Table i
    Strength on a stretch of 1-me, kg / cm Relative elongation,% (at
     Hot Modules indicate the percentage stretching of a strip of a sample of a crosslinked polymer after heating the polymer composition to 275 ° C and applying a load of 3.5 kg / cm to the crosslinked composition heated above the specified temperature.
    29.9
    35.3 27.9
    Example 2 A few more formulations are prepared as described in Example 1, containing either brassilic acid diallyl ester or phenylindacidicarboxylic acid as diallyl ester mixed with trimesinate as tridialdiallylbrasse.
    Diallyl ether
    In tab. 3 shows the mechanical 33.0 31.8 32.8 30.5 Example 3. According to the method described in examples 1 and 2, you get 40
    Triaplicisocyanurate
    Phenylindan diallyl ether
    Diallylbrassilate Table. 5 shows the mechanical
    purple ether. As in Example 1, the copolymer is a copolymer of ethylene with tetrafluoroethnene. All samples were directly compressed and irradiated for crosslinking with a dose of 10 Mrad according to the method of Example 1.
    Table 2
    the properties of these crosslinked formulations, Table 3, and the following crosslinked coefficients were irradiated: 28.5
    39.7 27., i Example 4. This example demonstrates the efficiency (1) of the effectiveness of the crosslinked polymer compositions of this invention, used as an insulating coating for wire. A sample consisting of a copolymer of ethylene with chlorotrifluoroethylene and 5.0% triallyl trimethylatte, and another sample consisting of a copolymer of ethylene with chlorotrifluoroethylene, 4% triallyltrimethrylate and 1.0% diallyl brasselate, were obtained according to a reference, according to a guideline, according to a reference. 1. To each mixture, 1.0% magnesium oxide and 0.3% TU pigment are added. Samples are obtained in the form of powder, then they are embedded through an extruder with a head temperature of 500 ° C, and the polymer leaves the extruder in the form of rods, which are then divided into balls and get balls, then extruded to the surface
    Tensile strength, kg / cm (room temperature, at a two-minute intern)
    Relative lengthening,% (room temperature, two-minute interval)
    T a b l and c a 5
    39.6 35.3 31.6 32,
    331 397
    551
    599
    125
    100
    12 copper wire coated with tin. The extrusion conditions for wire insulation are as follows: Temperature, ° C Zone cy Indra 1232 2260 3 265.6 Head 27 i Plunger er 271 The two insulated wires are then irradiated with a dose of 10 and 20 Mrad using a beam electron accelerator. The obtained insulated wire with irradiation with a cross-linked coating is then calcined, after which its mechanical and electrical properties are determined. The test results are shown in Table. 6. Table 6
    Flowability (room temperature, two-minute interval)
    Abrasion tape
    Tensile strength, kg / cm, 10 min)
    Relative elongation,% (250 C 10 min)
    Fluidity, kg / cm (, ten minute interval)
    Hot Modules, 7a
    Example 5. Samples consisting of a copolymer of ethylene with tetrafluoroethylene and different amounts of diallyl ester of phenyl dicane dicarboxylic acid and a tri-copolymer of ethylene with tetrafluoroethylene
    Phenylindicarboxylic acid diallyl ester Trimesic acid triallyl ester
    Magnesia oxide
    Titanium dioxide (pigment)
    349
    397
    331 396
    16.8 17.4 23.7 25.5
    4.92 5.76 172
    625
    242
    70
    6.25
    172
    5.76 62
    trimesic acid allrstate ester, obtained by the method described in example 1.
    The prepared samples have the composition given in table. 7. Table 7
    100
    100
    100
    3 I
    0.3
    0.3 0.3
    1190267112
    These samples are then re-coated onto the surface of the copper wire, and passed through a tin-coated extruder. perratura in the head, getting
    rods, which are then divided into balls. The extrusion conditions are given in Ki and the resulting balls are extruded - 5 tab. eight.
    Sample A is then extruded onto the surface of a wire having an outer diameter of 0.215 cm and a wall thickness of 0.048 cm. Sample B is extruded onto a wire with an outer diameter of 0.215 cm and a wall thickness of 0.06 cm and sample C is extruded into a wire with a diameter of 15 cm and thick wall OCT O. , 018 cm. Each of the samples is tensile strength, kg / cm (room temperature, with a two-minute interval) Relative elongation,% (room temperature, two-minute interval)
    Flowability (room temperature, two-minute interval)
    Tensile strength, kg / cm (250 ° C, 10 min)
    That blitz8
    The wire is irradiated with a 1.0 MeV electron beam accelerator. The obtained insulated film coated with a copolymer cross-linked under irradiation is burned and then tested for its mechanical and electrical properties. The results are shown in Table 9.
    T a b l and c a 9
    396,550,707
    143,108,106
    330 ЗЬ2 498
    13
    Relative elongation,% (10 min)
    Fluidity, kg / cm (, ten minute interval)
    权利要求:
    Claims (2)
    [1]
    Hot Modules,% The proposed crosslinking compositions in terms of relative elongation and strain resistance are significantly superior to compositions containing each ester as a crosslinkable agent. Resistance to deformation, especially at elevated temperatures, is crucial in a whole range of applications, for example, for wire or cable insulation. The invention Polymer composition based on fluorocarbon polymer containing polycarbonate ester polycarbonate to slots, characterized in that, in order to improve elasticity and resistance to deformation, it contains a fluorocarbon polymer, it contains a combination of ethylene with tetrafluoroethylene, or any other means that does not contain the same pattern, and it has not been combined with the same pattern and has to use the same. polycarboxylic acid contains a mixture of triallyl acid ester, selected from the group including 90267114
    Continued table. 9, trimellitic, trimesic and isocyanuric acids with diallyl ether of brassilic or phenylindicarboxylic acid at a ratio in a mixture of triallyl ether to diaplyl ether 1: 4–4: 1 with the following content of the components of the composition, wt.%: An ethylene – copolymer ethereal pattern. 97 A mixture of triallyl ester of polycarboxylic acid and diaplyl ether of brassilic or fenshndicarboxylic acid B ratio of 1: 4-4: 1 3-g8 Sources of information taken into account during the examination 1. US patent number 3763222, k . 260-475, published. 1973.
    [2]
    2. US patent number 3840619, cl. 260-878, published. 1974 (prototype).
    类似技术:
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    同族专利:
    公开号 | 公开日
    NO743554L|1975-04-28|
    NL7412691A|1975-04-03|
    FR2246590A1|1975-05-02|
    JPS5062241A|1975-05-28|
    AU7386574A|1976-04-08|
    ZA746210B|1975-11-26|
    DE2445795A1|1975-04-10|
    US3911192A|1975-10-07|
    IT1022378B|1978-03-20|
    AT331509B|1976-08-25|
    FR2246590B1|1978-11-24|
    DE2445795C2|1985-08-01|
    ATA786074A|1975-11-15|
    SE7412246L|1975-04-02|
    CA1035083A|1978-07-18|
    CH619252A5|1980-09-15|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3141850A|1964-07-21|Insulating composition containing poly- |
    US2845404A|1955-04-28|1958-07-29|Us Rubber Co|Internally plasticized polymers of vinyl chloride|
    US2958672A|1956-11-19|1960-11-01|Du Pont|Curing process for high molecular weight polymers involving the use of free radical generators and free radical acceptors and product thereof|
    NL231223A|1957-09-10|1900-01-01|
    NL253378A|1959-07-08|
    US3230203A|1960-03-30|1966-01-18|Hoechst Ag|Process for the manufacture of copolymers of vinyl chloride|
    US3351604A|1965-07-01|1967-11-07|Gen Electric|Compositions of vinyl halide resins, triallyl cyanurate, and trioctyl trimellitates and cured products therefrom|US4078114A|1976-03-26|1978-03-07|International Telephone And Telegraph Corporation|Wire coated with diallyl esters of dicarboxylic acids|
    US3995091A|1974-11-29|1976-11-30|International Telephone And Telegraph Corporation|Wire coated with a fluorocarbon polymer cross-linked with esters of sulfonyl dibenzoic acid|
    US4353961A|1977-09-14|1982-10-12|Raychem Corporation|Shaped article from crosslinked fluorocarbon polymer|
    US4121001A|1977-01-14|1978-10-17|Raychem Corporation|Crosslinking agent for polymers and wire construction utilizing crosslinked polymers|
    USRE31103E|1977-01-14|1982-12-14|Raychem Corporation|Crosslinking agent for polymers and wire construction utilizing crosslinked polymers|
    JPS6210244B2|1978-11-18|1987-03-05|Nippon Kasei Chem|
    US4444816A|1980-12-03|1984-04-24|Raychem Corporation|Radiation cross-linking of polyamides|
    US4770937A|1981-06-26|1988-09-13|Hitachi Cable, Ltd.|Fluorine-containing elastomeric electric insulating material and insulated electric wire coated therewith|
    US4521485A|1982-09-15|1985-06-04|Raychem Corporation|Electrical insulation|
    US4678709A|1982-09-15|1987-07-07|Raychem Corporation|Electrical insulation|
    US4637955A|1983-11-07|1987-01-20|High Voltage Engineering Corporation|Wire insulated with a fluorocarbon polymer composition|
    US4595724A|1984-01-24|1986-06-17|Amp Incorporated|Flame retardant sealant|
    US4539228A|1984-10-29|1985-09-03|Arnold Lazarus|Method of extending useful life of instrument strings|
    US5059483A|1985-10-11|1991-10-22|Raychem Corporation|An electrical conductor insulated with meit-processed, cross-linked fluorocarbon polymers|
    US5057345A|1989-08-17|1991-10-15|Raychem Corporation|Fluoroopolymer blends|
    GB9404390D0|1994-03-07|1994-04-20|Bicc Plc|Manufacture of electric cables|
    US6207277B1|1997-12-18|2001-03-27|Rockbestos-Surprenant Cable Corp.|Multiple insulating layer high voltage wire insulation|
    WO2002084674A2|2001-04-17|2002-10-24|Judd Wire, Inc.|A multi-layer insulation system for electrical conductors|
    WO2015149223A1|2014-03-31|2015-10-08|Dow Global Technologies Llc|Crosslinkable polymeric compositions with diallylamide crosslinking coagents, methods for making the same, and articles made therefrom|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    US402302A|US3911192A|1973-10-01|1973-10-01|Coated wire products|
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