CN112979854B - Polyolefin elastomer containing siloxane and preparation method and application thereof - Google Patents
Polyolefin elastomer containing siloxane and preparation method and application thereof Download PDFInfo
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- 229920006124 polyolefin elastomer Polymers 0.000 title claims abstract description 50
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical group N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 11
- 150000003254 radicals Chemical class 0.000 claims abstract description 6
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 3
- 239000004711 α-olefin Substances 0.000 claims description 43
- 239000003063 flame retardant Substances 0.000 claims description 30
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 23
- 239000005977 Ethylene Substances 0.000 claims description 23
- 238000012545 processing Methods 0.000 claims description 20
- 239000003999 initiator Substances 0.000 claims description 17
- 229920001577 copolymer Polymers 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 8
- 239000012968 metallocene catalyst Substances 0.000 claims description 7
- 229920001296 polysiloxane Polymers 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 4
- 238000009717 reactive processing Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000011954 Ziegler–Natta catalyst Substances 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 239000012934 organic peroxide initiator Substances 0.000 claims 1
- 239000000178 monomer Substances 0.000 abstract description 22
- 239000000463 material Substances 0.000 abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 8
- 238000002485 combustion reaction Methods 0.000 abstract description 8
- 229920000098 polyolefin Polymers 0.000 abstract description 7
- 239000000377 silicon dioxide Substances 0.000 abstract description 4
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 150000001336 alkenes Chemical class 0.000 abstract 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 30
- 239000000047 product Substances 0.000 description 27
- 229920000642 polymer Polymers 0.000 description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 12
- 239000003963 antioxidant agent Substances 0.000 description 12
- 230000003078 antioxidant effect Effects 0.000 description 12
- 238000006116 polymerization reaction Methods 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 6
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 5
- 229910007928 ZrCl2 Inorganic materials 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000010907 mechanical stirring Methods 0.000 description 5
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000002411 thermogravimetry Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 239000012796 inorganic flame retardant Substances 0.000 description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- -1 siloxane chain Chemical group 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 3
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 2
- RIMXEJYJXDBLIE-UHFFFAOYSA-N 6-bromohex-1-ene Chemical compound BrCCCCC=C RIMXEJYJXDBLIE-UHFFFAOYSA-N 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- XYBQTTAROZGWOZ-UHFFFAOYSA-N bis[[hydroxy(dimethyl)silyl]oxy]-dimethylsilane Chemical compound C[Si](C)(O)O[Si](C)(C)O[Si](C)(C)O XYBQTTAROZGWOZ-UHFFFAOYSA-N 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- XQOLMPJRVURWFY-UHFFFAOYSA-N dichloro-hex-5-enyl-methylsilane Chemical compound C[Si](Cl)(Cl)CCCCC=C XQOLMPJRVURWFY-UHFFFAOYSA-N 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- PFEAZKFNWPIFCV-UHFFFAOYSA-N hydroxy-[hydroxy(dimethyl)silyl]oxy-dimethylsilane Chemical compound C[Si](C)(O)O[Si](C)(C)O PFEAZKFNWPIFCV-UHFFFAOYSA-N 0.000 description 2
- NGTQJLNKMOCOQA-UHFFFAOYSA-M magnesium;hex-1-ene;bromide Chemical compound [Mg+2].[Br-].[CH2-]CCCC=C NGTQJLNKMOCOQA-UHFFFAOYSA-M 0.000 description 2
- 239000005055 methyl trichlorosilane Substances 0.000 description 2
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052799 carbon Chemical group 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- LJWHIRABJHRRDD-UHFFFAOYSA-N hydroxy-[[methoxy(dimethyl)silyl]oxy-dimethylsilyl]oxy-dimethylsilane Chemical compound CO[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O LJWHIRABJHRRDD-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- 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
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/08—Copolymers of ethene
- C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
- C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a siloxane-containing polyolefin elastomer and a preparation method and application thereof. The polyolefin elastomer can be prepared from olefin monomers by a copolymerization method, and can also be prepared by a free radical grafting method of polyolefin. The prepared polyolefin elastomer can generate a large amount of silicon dioxide and carbon residue after combustion due to the siloxane component, so that the material has a flame retardant function.
Description
Technical Field
The invention relates to a polyolefin elastomer and a preparation method and application thereof, in particular to a preparation method and application of a polyolefin elastomer with siloxane-containing side groups.
Background
The polyolefin elastomer is a high value-added polyolefin material, has the characteristics of good chemical stability, excellent corrosion resistance, strong electrical insulation, excellent processability and the like of the polyolefin material, has the characteristic of excellent low-temperature performance of rubber, and is widely applied to the fields of wires and cables, building waterproof materials, household appliances, automobile manufacturing, medical treatment and the like. As the polyolefin belongs to flammable materials, huge fire hazard exists in practical application, and the wider application of the polyolefin elastomer is restricted. Therefore, flame retardant properties become one of the important properties of polyolefin elastomers. With the continuous development of society, the safety standard of the manufacturing industry for rubber and plastic products is gradually improved, and the efficient flame-retardant modification of polyolefin elastomers is urgent. Most of the flame retardants added to the early elastomer products are halogen flame retardants, but the decomposition products of the halogen flame retardants after combustion contain many harmful substances, and the application thereof is gradually limited. At present, the flame retardant of the elastomer material mainly takes high efficiency, low smoke and no toxicity as the development direction, and the research and application of various halogen-free flame retardants also become the most active research field for flame retardant modification of polyolefin elastomers. For example, phosphorus-based flame retardants can exhibit flame retardant properties in the condensed or gas phase, promote char formation, and insulate the polymer matrix from heat, fire, and oxygen to achieve flame retardant functionality. For another example, the intumescent composite flame retardant generates gaseous water and non-combustible gas during combustion to expand the polymer in a molten state, and meanwhile, the polyol and ester in the flame retardant form inorganic matters and carbon residues during decomposition and carbonization, so that air is blocked and combustion is inhibited. However, at present, the most common halogen-free flame retardant systems are also inorganic metal oxides represented by magnesium hydroxide. The inorganic flame retardant is dispersed in the polyolefin elastomer in a physical mixing mode, and the inorganic flame retardant plays a role in flame retardance in a condensed phase or a gas phase through physical or chemical changes. Besides good combustion inhibition effect, the inorganic flame retardant also has the advantages of low smoke, no toxicity and environmental protection, and is the trend of the development of the flame retardant in the future; the disadvantage is that the inorganic flame retardant usually needs higher addition amount (more than 50%) to achieve better flame retardant effect, which undoubtedly has great influence on the elasticity of the product and is not beneficial to the optimization of the product performance. In addition, the organic silicon flame retardant is also a halogen-free flame retardant, and the flame retardant mechanism of the organic silicon flame retardant is that an inorganic layer of silicon dioxide and carbide can be generated during combustion, so that the organic silicon flame retardant plays a role in blocking air and heat, and thus, the combustion is inhibited. For example, silicone resins and silicone rubbers have excellent flame retardant properties by themselves, but have the disadvantage of being expensive.
Disclosure of Invention
According to the invention, the siloxane chain segment is chemically connected to the polyolefin elastomer side group, so that the polyolefin elastomer substrate is endowed with a flame-retardant function, and the application of the siloxane chain segment in the field of flame-retardant materials is greatly widened.
The invention provides a polyolefin elastomer with siloxane-containing side groups, which has the following structure:
wherein R is1Is C1~C20Linear, branched or isomerized alkyl, or C6~C20Aryl of (A), R2Is H or CH3R3 is C1~C12The straight-chain alkane of (1); x is 100-100000, preferably x is 500-50000; y is 100-50000, preferably y is 500-20000; z is 0.0001x to 0.2x, preferably 0.001x to 0.1 x; m is a positive integer of 1 to 3, and n is a positive integer of 1 to 100.
Another object of the present invention is to provide a method for preparing the above polyolefin elastomer, comprising the steps of:
copolymerizing ethylene and alpha-olefin (I) and alpha-olefin (II) having the following structures in the presence of a catalyst to obtain a silicone-containing polyolefin elastomer;
α -olefin (I):
CH2=CH-R3
α -olefin (II):
wherein R is1Is C1~C20Linear, branched or isomerized alkyl, or C6~C20Or R is an aromatic radical of1Absent, with silicon atoms directly attached to carbon atoms in ethylene, preferably R1Is C2~C8A straight-chain alkyl group of (A), or C6~C14An aromatic group of (a); r2Is H or CH3;R3Is C1~C12Linear alkanes of (1), preferably R3Is C1~C8The straight-chain alkane of (1); m is a positive integer of 1-3, preferably m is 2 or 3; n is a positive integer of 1 to 100, preferably 1 to 20.
Further, the catalyst comprises a Ziegler-Natta catalyst or a metallocene catalyst.
Further, when the polyolefin elastomer of the present invention is prepared by the above polymerization method, the α -olefin (I) is used in an amount of 1 to 500 parts by mole, preferably 20 to 200 parts by mole, relative to 100 parts by mole of the ethylene monomer; the amount of the alpha-olefin (II) is 0.01 to 50 parts by mole, preferably 0.1 to 20 parts by mole. The polymerization conditions include: the polymerization pressure is 0.1-6 MPa, preferably 0.1-4 MPa; the polymerization temperature is 30-150 ℃, preferably 60-120 ℃; the polymerization time is 0.1 to 6 hours, preferably 0.2 to 3 hours.
The preparation method of the polyolefin elastomer can also be prepared by the following steps: the method comprises the following steps:
carrying out copolymerization reaction on ethylene and alpha-olefin (I) with the structure in the presence of a catalyst to obtain an ethylene/alpha-olefin (I) copolymer;
obtaining a siloxane-containing polyolefin elastomer by performing free radical grafting reaction on an ethylene/alpha-olefin (I) copolymer and alpha-olefin (III) with the following structure under the action of an initiator;
α -olefin (I):
CH2=CH-R3
α -olefin (III):
wherein R is1’Is C6~C20Aryl or R of1’Absent, with silicon atoms directly bound to carbon atoms in ethylene, R2Is H or CH3,R3Is C1~C12The straight-chain alkane of (1); preferably R1’Is C6~C14Further preferably R1’Is C6Aryl or R1’Absent, with silicon atoms directly bound to carbon atoms in ethylene, R2Is H or CH3,R3Is C1~C8The straight-chain alkane of (1); m is a positive integer of 1-3, preferably m is 2 or 3; n is a positive integer of 1 to 100, preferably 1 to 20.
Further, the initiator includes an organic peroxide-based initiator or an azo-based initiator.
Further, the organic or oxide type initiator includes dicumyl peroxide; the azo initiator includes 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane.
Further, when the polyolefin elastomer of the present invention is produced by the above-mentioned radical grafting method, the α -olefin (III) is used in an amount of 0.1 to 100 parts by mass, preferably 1 to 50 parts by mass, relative to 100 parts by mass of the ethylene/α -olefin (I) copolymer; the amount of the initiator is 0.01 to 1 part by mass, preferably 0.05 to 0.5 part by mass. The conditions of the radical grafting method include: the raw materials are mixed and then added into reactive processing equipment, and the processing temperature is 120-250 ℃, preferably 150-210 ℃. The reactive processing equipment comprises one of a single-screw extruder, a double-screw extruder, an open mill and an internal mixer.
The invention also provides the application of the siloxane-containing polyolefin elastomer as a raw material of the flame-retardant polyolefin elastomer.
The invention not only can solve the problem of poor compatibility between the added flame retardant and the polyolefin elastomer, but also can ensure the good flexibility of the polyolefin elastomer; the siloxane component of the polymer side group can play a role of a silicon flame retardant when the polyolefin elastomer is burnt, and the optimized flame retardant function of the polyolefin elastomer is endowed by generating a silicon dioxide inorganic layer and a carbide in situ during the burning.
Drawings
FIG. 1 is a photograph of the experimental residue of thermogravimetric analysis of a sample of example 3 (nitrogen experimental atmosphere).
FIG. 2 is a photograph of the experimental residue of the thermogravimetric analysis of the sample of example 3 (air experimental atmosphere).
FIG. 3 is a graph of the thermal weight loss of a polyolefin elastomer.
Detailed Description
The following examples are presented as further illustrations and are not intended to limit the scope of the claims. The alpha-olefins having the formula A, B, C used in the examples of the present invention were obtained by the following routes or manners.
For the synthesized alpha-olefin monomer, the application provides a conventional synthesis method, and the alpha-olefin monomer is not limited.
(1) α -olefin monomer a:
adding 3.5g of magnesium chips and 0.8g of 6-bromo-1-hexene into a 500mL three-neck flask, adding 200mL of dried tetrahydrofuran into the flask under the nitrogen atmosphere, starting stirring, adding 50mg of iodine into the reaction solution, stirring for 30min at room temperature, then slowly dropwise adding 25.3g of 6-bromo-1-hexene, and carrying out reflux reaction for 6 hours until the solid in the reaction flask disappears. Filtering under the protection of nitrogen, and collecting filtrate to obtain 5-hexenyl magnesium bromide solution.
Adding 100mL of dry tetrahydrofuran into a 500mL three-neck flask, weighing 12.1g of methyltrichlorosilane into the flask under the nitrogen atmosphere, starting stirring, slowly dropwise adding the 5-hexenyl magnesium bromide solution prepared in the previous step into the flask, stirring at room temperature for reaction for 12 hours, and carrying out reduced pressure distillation and refining to obtain the 5-hexenyl methyl dichlorosilane.
Dissolving an excessive amount of 5-methoxy-1, 1,3,3,5, 5-hexamethyl-1-hydroxytrisiloxane (CAS No.49778-22-5) in 100mL of anhydrous tetrahydrofuran, slowly dripping the dissolved 5-hexenylmethyl-dichlorosilane into the anhydrous tetrahydrofuran, reacting at 0 ℃ for 24 hours, distilling the tetrahydrofuran and excessive unreacted reactants under reduced pressure, and obtaining the alpha-olefin monomer A at the bottom of a reaction bottle. The structural formula is as follows:
(2) α -olefin monomer B:
after 5g of magnesium chips and 100mL of anhydrous tetrahydrofuran were put into a 250mL three-necked flask, 10g of 4-chlorostyrene was added dropwise thereto, and the reaction was carried out for 2 hours, the resulting suspension was transferred to a constant pressure dropping funnel, and the suspension was added dropwise to a three-necked flask containing 50mL of anhydrous tetrahydrofuran and 11.56g of methyltrichlorosilane and reacted at room temperature for 20 hours. And (3) distilling under reduced pressure to remove tetrahydrofuran, filtering to obtain a crude product, continuing distilling under reduced pressure, and collecting fractions at 40-60 ℃.1mol of the collected product is taken and dissolved in 100mL of anhydrous tetrahydrofuran, slowly dropped into 2mol of hexamethyl-1, 5-dihydroxy trisiloxane (CAS No.3663-50-1), reacted for 24 hours at 0 ℃, and then the tetrahydrofuran is removed by reduced pressure distillation to obtain the alpha-olefin monomer B. The structural formula is as follows:
(3) α -olefin monomer C:
after 5g of magnesium chips and 100mL of anhydrous tetrahydrofuran were put into a 250mL three-necked flask, 10g of 4-chlorostyrene was added dropwise thereto, and the mixture was reacted for 2 hours, the resulting suspension was transferred to a constant pressure dropping funnel, and the mixture was added dropwise to a three-necked flask containing 50mL of anhydrous tetrahydrofuran and 12.7g of tetrachlorosilane and reacted for 20 hours at room temperature. And (3) distilling under reduced pressure to remove tetrahydrofuran, filtering to obtain a crude product, continuing distilling under reduced pressure, and collecting fractions at 40-60 ℃.1mol of the collected product is taken and dissolved in 100mL of anhydrous tetrahydrofuran, slowly dropped into 3mol of 1,1,3, 3-tetramethyl-1, 3-disiloxane diol (CAS No.1118-15-6) to react for 24 hours at 0 ℃, and the tetrahydrofuran is removed by reduced pressure distillation to obtain the alpha-olefin monomer C. The structural formula is as follows:
comparative example 1
In a 500mL reactor with mechanical stirring, 100mL of toluene, 4mmol of methylaluminoxane and 2. mu. mol of metallocene catalyst C were added2H4(Ind)2ZrCl2An ethylene/propylene mixed gas (0.5 MPa) was introduced thereinto, wherein the ratio of ethylene to propylene was 1: 1(v/v), and the reaction was carried out at 60 ℃ for 1 hour. The polymerization product was collected, washed and dried to obtain 28.5g of an ethylene-propylene copolymer.
The ethylene content of the polymer was 59.7 mol% and the propylene content was 40.3 mol%. The basic polymer properties are shown in Table 1.
Comparative example 2
In a 500mL reactor with mechanical stirring, 100mL of toluene, 20mL of 1-octene, 4mmol of methylaluminoxane and 2. mu. mol of metallocene catalyst C were added2H4(Ind)2ZrCl2And introducing ethylene under 0.3MPa to react at 60 ℃ for 0.5 hour. The polymerization product was collected, washed and dried to obtain 15.0g of an ethylene/1-octene copolymer.
The ethylene content of the polymer was 75.5 mol%, and the 1-octene content was 24.5 mol%. The basic polymer properties are shown in Table 1.
Example 1
In a 500mL reactor with mechanical stirring, 100mL of toluene, 12g of alpha-olefin monomer A, 4mmol of methylaluminoxane and 2. mu. mol of metallocene catalyst C were added2H4(Ind)2ZrCl2An ethylene/propylene mixed gas (0.5 MPa) was introduced thereinto, wherein the ratio of ethylene to propylene was 1: 1(v/v), and the reaction was carried out at 60 ℃ for 1 hour. The polymerization product was collected, washed and dried to obtain 17.6g of a silicone-containing polyolefin elastomer.
The polymer had an ethylene content of 55.2 mol%, a propylene content of 38.7 mol% and an alpha-olefin monomer A content of 6.1 mol%. The basic polymer properties are shown in Table 1.
Example 2
In a 500mL reactor with mechanical stirring, 100mL of toluene, 20mL of 1-octene, 20g of alpha-olefin monomer A, 10mmol of methylaluminoxane, 4. mu. mol of metallocene catalyst C2H4(Ind)2ZrCl2And introducing ethylene under 0.3MPa to react at 60 ℃ for 0.5 hour. The polymerization product was collected, washed and dried to obtain 18.2g of a silicone-containing polyolefin elastomer.
The polymer had an ethylene content of 65.4 mol%, a 1-octene content of 21.5 mol%, and an alpha-olefin monomer A content of 13.1 mol%. The basic polymer properties are shown in Table 1.
Example 3
In a 500mL reactor with mechanical stirring, 100mL of toluene, 20mL of 1-octene, 10g of alpha-olefin monomer B, 15mmol of methylaluminoxane, 4. mu. mol of metallocene catalyst C2H4(Ind)2ZrCl2And introducing ethylene under 0.3MPa to react at 60 ℃ for 0.5 hour. The polymerization product was collected, washed and dried to obtain 14.7g of a silicone-containing polyolefin elastomer.
The polymer had an ethylene content of 72.3 mol%, a 1-octene content of 20.9 mol%, and an alpha-olefin monomer B content of 6.8 mol%. The basic polymer properties are shown in Table 1.
Example 4
100 parts by mass of the ethylene-propylene copolymer synthesized in comparative example 1, 0.1 part of 1010 (antioxidant), 0.2 part of 168 (antioxidant), 0.1 part of dicumyl peroxide (initiator), 15 parts of the α -olefin monomer B of the present invention were mixed, and the mixture was then charged into an internal mixer (HAAKE, germany) and processed. The processing temperature is 150 ℃, the set rotating speed is 60rpm, and the processing time is 3min, so that the siloxane-containing polyolefin elastomer product is obtained. The product structure and properties are shown in table 1.
Example 5
100 parts by mass of the ethylene-propylene copolymer synthesized in comparative example 1, 0.1 part of 1010 (antioxidant), 0.2 part of 168 (antioxidant), 0.2 part of dicumyl peroxide (initiator), 30 parts of the α -olefin monomer B of the present invention were mixed, and the mixture was then charged into an internal mixer (HAAKE, germany) and processed. The processing temperature is 150 ℃, the set rotating speed is 60rpm, and the processing time is 4min, so that the siloxane-containing polyolefin elastomer product is obtained. The product structure and properties are shown in table 1.
Example 6
100 parts by mass of the ethylene-propylene copolymer synthesized in comparative example 1, 0.1 part of 1010 (antioxidant), 0.2 part of 168 (antioxidant), 0.15 part of 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane (initiator), 35 parts of the α -olefin monomer B of the present invention were mixed, and the mixture was then charged into an internal mixer (HAAKE, germany) for processing. The processing temperature is 150 ℃, the set rotating speed is 60rpm, and the processing time is 4min, so that the siloxane-containing polyolefin elastomer product is obtained. The product structure and properties are shown in table 1.
Example 7
100 parts by mass of the ethylene/1-octene copolymer synthesized in comparative example 2, 0.1 part of 1010 (antioxidant), 0.2 part of 168 (antioxidant), 0.15 part of 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane (initiator), 30 parts of the α -olefin monomer B of the present invention were mixed, and the mixture was then charged into an internal mixer (HAAKE, germany) for processing. The processing temperature is 170 ℃, the set rotating speed is 60rpm, and the processing time is 4min, so that the siloxane-containing polyolefin elastomer product is obtained. The product structure and properties are shown in table 1.
Example 8
100 parts by mass of the ethylene/1-octene copolymer synthesized in comparative example 2, 0.1 part 1010 (antioxidant), 0.2 part 168 (antioxidant), 0.2 part 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane (initiator), 35 parts of the α -olefin monomer C of the present invention were mixed, and the mixture was then charged into an internal mixer (HAAKE, germany) for processing. The processing temperature is 170 ℃, the set rotating speed is 60rpm, and the processing time is 4min, so that the siloxane-containing polyolefin elastomer product is obtained. The product structure and properties are shown in table 1.
Example 9
100 parts by mass of the ethylene/1-octene copolymer synthesized in comparative example 2, 0.1 part of 1010 (antioxidant), 0.2 part of 168 (antioxidant), 0.1 part of 2, 5-dimethyl-2, 5-di (t-butylperoxy) hexane (initiator), 15 parts of the α -olefin monomer C of the present invention were mixed, and the mixture was then charged into an internal mixer (HAAKE, germany) for processing. The processing temperature is 170 ℃, the set rotating speed is 60rpm, and the processing time is 2min, so that the siloxane-containing polyolefin elastomer product is obtained. The product structure and properties are shown in table 1.
Example 10
100 parts by mass of the ethylene/1-octene copolymer synthesized in comparative example 2 and 100 parts by mass of the silicone-containing polyolefin elastomer synthesized in example 2 were mixed, and the mixture was then charged into an internal mixer (HAAKE, Germany) and processed. The processing temperature is 170 ℃, the set rotating speed is 60rpm, and the processing time is 1min, so that the product is obtained. The product structure and properties are shown in table 1.
TABLE 1 Polymer Structure and Properties
It can be seen that the conventional polyolefins (comparative example 1, comparative example 2) had no flame retardant function and the weight of the residue after the completion of the burning test was 0. The siloxane-containing polyolefin elastomer of the present invention has residues remained after the combustion test is completed, and it can be observed in fig. 1 and 2 that a large amount of residues remained in the sample dish after the thermogravimetric analysis (TGA) test of the siloxane-containing polyolefin elastomer of the present invention (example 3), which indicates that the sample has obvious flame retardant property.
The thermogravimetric analysis of the residual weight percentages for all samples of the inventive examples are listed in table 1. The thermogravimetric curves of comparative example 1, comparative example 2, examples 3, 6, and 9 are shown in FIG. 3. Because the siloxane component is introduced into the polymer, the polymer can not be completely burnt out when subjected to a thermal weight loss test, and a certain proportion of residues (silicon dioxide and carbon residue) are still remained at 700 ℃. With the increase of the content of siloxane, the proportion of residues after the thermal weight loss test is gradually increased, and the flame retardant property is better.
The flame-retardant polyolefin elastomer prepared by the invention can be blended with common polyolefin to endow the common polyolefin with a flame-retardant function, for example, example 10 is obtained by blending the products of example 2 and comparative example 2, and also shows obvious flame-retardant effect. Therefore, the polyolefin elastomer is a novel material with a self-flame-retardant function, and can be used as a flame-retardant material alone or mixed with other materials.
Meanwhile, the obtained polyolefin elastomer keeps the advantage of low glass transition temperature, and because the introduced siloxane component is positioned on the polymer side group and has proper content, the flexibility of the polyolefin elastomer main chain is not obviously influenced, so that the polyolefin elastomer can still keep elasticity at low temperature.
Claims (6)
1. A method of preparing a silicone-containing polyolefin elastomer, characterized by having the structure:
wherein R is1Is C6~C20Aryl of (A), R2Is H or CH3,R3Is C1~C12The straight-chain alkane of (1); x is 100-100000, y is 100-50000, and z is 0.0001-0.2 x; m is a positive integer of 1-3, n is a positive integer of 1-100;
the preparation method comprises the following steps: carrying out copolymerization reaction on ethylene and alpha-olefin (I) with the structure in the presence of a catalyst to obtain an ethylene/alpha-olefin (I) copolymer;
obtaining a siloxane-containing polyolefin elastomer by performing free radical grafting reaction on an ethylene/alpha-olefin (I) copolymer and alpha-olefin (III) with the following structure under the action of an initiator;
α -olefin (I):
CH2=CH-R3
α -olefin (III):
in the formula, R1’Is C6~C20Aryl of (A), R2Is H or CH3,R3Is C1~C12The straight-chain alkane of (1); m is a positive integer of 1 to 3, and n is a positive integer of 1 to 100.
2. The method of claim 1, wherein R is1’Is C6~C14An aromatic group of (a); r2Is H or CH3,R3Is C1~C8The straight-chain alkane of (1); m is 2 or 3, and n is a positive integer of 1-20.
3. The method according to claim 1, wherein the initiator comprises an organic peroxide initiator or an azo initiator.
4. The method of claim 1, wherein the catalyst comprises a Ziegler-Natta catalyst or a metallocene catalyst.
5. The production method according to claim 1, wherein the α -olefin (III) is used in an amount of 0.1 to 100 parts by mass relative to 100 parts by mass of the ethylene/α -olefin (I) copolymer; the amount of the initiator is 0.01-1 part by mass; the conditions of the radical grafting reaction include: mixing the raw materials, and adding the mixture into reactive processing equipment, wherein the processing temperature is 120-250 ℃; the reactive processing equipment comprises one of a single-screw extruder, a double-screw extruder, an open mill and an internal mixer.
6. Use of the silicone-containing polyolefin elastomer prepared by the preparation method according to any one of claims 1 to 5 as a raw material of a flame-retardant polyolefin elastomer.
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