CN1322039C - Expandable resin beads of styrene-modified straight-chain and low-density polyethylene, process for production thereof, pre-expand beads, and foams - Google Patents
Expandable resin beads of styrene-modified straight-chain and low-density polyethylene, process for production thereof, pre-expand beads, and foams Download PDFInfo
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- CN1322039C CN1322039C CNB2004800032702A CN200480003270A CN1322039C CN 1322039 C CN1322039 C CN 1322039C CN B2004800032702 A CNB2004800032702 A CN B2004800032702A CN 200480003270 A CN200480003270 A CN 200480003270A CN 1322039 C CN1322039 C CN 1322039C
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- 229920001684 low density polyethylene Polymers 0.000 title claims abstract description 16
- 239000004702 low-density polyethylene Substances 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims description 46
- 239000011324 bead Substances 0.000 title claims description 12
- 239000012508 resin bead Substances 0.000 title abstract 2
- 238000004519 manufacturing process Methods 0.000 title description 6
- 239000006260 foam Substances 0.000 title description 4
- 230000008569 process Effects 0.000 title description 2
- 229920005989 resin Polymers 0.000 claims abstract description 146
- 239000011347 resin Substances 0.000 claims abstract description 146
- 239000004088 foaming agent Substances 0.000 claims abstract description 11
- 229920000578 graft copolymer Polymers 0.000 claims abstract 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 208
- 239000002245 particle Substances 0.000 claims description 201
- 239000000178 monomer Substances 0.000 claims description 89
- 238000006116 polymerization reaction Methods 0.000 claims description 89
- 239000004793 Polystyrene Substances 0.000 claims description 67
- 229920002223 polystyrene Polymers 0.000 claims description 67
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 49
- 239000011342 resin composition Substances 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 27
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 27
- 239000007858 starting material Substances 0.000 claims description 25
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 238000002360 preparation method Methods 0.000 claims description 17
- 239000006185 dispersion Substances 0.000 claims description 16
- 239000011159 matrix material Substances 0.000 claims description 9
- 238000005187 foaming Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229920005990 polystyrene resin Polymers 0.000 abstract description 32
- 238000002156 mixing Methods 0.000 abstract description 25
- 229920013716 polyethylene resin Polymers 0.000 abstract description 4
- -1 polyethylene Polymers 0.000 description 75
- 239000004698 Polyethylene Substances 0.000 description 68
- 229920000573 polyethylene Polymers 0.000 description 68
- 239000000843 powder Substances 0.000 description 49
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 43
- 239000012736 aqueous medium Substances 0.000 description 18
- 229920000642 polymer Polymers 0.000 description 16
- 230000035939 shock Effects 0.000 description 16
- 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 15
- 230000000052 comparative effect Effects 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 238000011049 filling Methods 0.000 description 10
- 230000008859 change Effects 0.000 description 9
- 238000001816 cooling Methods 0.000 description 9
- XZTWHWHGBBCSMX-UHFFFAOYSA-J dimagnesium;phosphonato phosphate Chemical compound [Mg+2].[Mg+2].[O-]P([O-])(=O)OP([O-])([O-])=O XZTWHWHGBBCSMX-UHFFFAOYSA-J 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 238000000746 purification Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000000725 suspension Substances 0.000 description 8
- 239000003999 initiator Substances 0.000 description 7
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 7
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000001273 butane Substances 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 238000010559 graft polymerization reaction Methods 0.000 description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 229920001903 high density polyethylene Polymers 0.000 description 4
- 239000004700 high-density polyethylene Substances 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 239000004744 fabric Substances 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000003505 polymerization initiator Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
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- 239000012159 carrier gas Substances 0.000 description 2
- 229920006037 cross link polymer Polymers 0.000 description 2
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011810 insulating material Substances 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000006166 lysate Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000013518 molded foam Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- YIWGJFPJRAEKMK-UHFFFAOYSA-N 1-(2H-benzotriazol-5-yl)-3-methyl-8-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carbonyl]-1,3,8-triazaspiro[4.5]decane-2,4-dione Chemical compound CN1C(=O)N(c2ccc3n[nH]nc3c2)C2(CCN(CC2)C(=O)c2cnc(NCc3cccc(OC(F)(F)F)c3)nc2)C1=O YIWGJFPJRAEKMK-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- 241001253206 Andrias Species 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019439 ethyl acetate Nutrition 0.000 description 1
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- 235000012245 magnesium oxide Nutrition 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical group CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000005477 standard model Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
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- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
Abstract
Expandable resin beads of styrene-modified, straight -chain, and low-density polyethylene, which comprise both a base resin obtained by blending a non-crosslinked, straight-chain, and low-density polyethylene resin component with a polystyrene resin component in an amount exceeding 300 parts by weight and up to 1000 parts by weight per 100 parts by weight of the polyethylene resin component and a volatile foaming agent and in which the base resin contains 2 to 40 wt% of a gel consisting of a graft polymer composed of the low-density polyethylene resin component and the polystyrene resin component.
Description
Technical field
The present invention relates to phenylethene modified linear low density polyethylene base resin expanded particle, its preparation method, pre-expanded beads and expanded molded article.
Background technology
Therefore the polyvinyl resin foam is commonly used for wrapping material owing to have the oil-proofness and the shock resistance of snappiness, excellence.Yet the polyvinyl resin foam materials also has the low and low shortcoming of compressive strength of hardness.On the other hand, the hardness height of polystyrene based resin foam, but have frangible shortcoming.
In order to overcome these shortcomings, special public clear 51 (1976)-No. 46138 communiques and clear 62 (1987)-No. 59642 communiques of Te Kai disclose by styrene monomer is filled into and have carried out the method that polymerization obtains styrene-modified polyethylene base resin expanded particle in the polyvinyl resin.
The example that is used for the polyvinyl resin of this method mainly comprises new LDPE (film grade), high density polyethylene(HDPE) and vinyl-vinyl acetate copolymer.In most cases with polyethylene crosslinking to improve the physicals of its formability and moulded products.The poly crosslinked foam film strength that strengthened has also strengthened the tensile strength of film in foaming (expansion molding) process, so can prevent film rupture, and can increase rate of expansion.
Therefore, can obtain the expanded molded article of good appearance, and the resistance to impact shock of expanded molded article is strengthened also.But this method need be used the precrosslink polyethylene, perhaps need cross-linking step be set with polyethylene crosslinking after temperature further raises finally in the styrene monomer polyreaction.
In order to address the above problem, the patent No. is that 2668384 Japanese Patent also discloses a kind of all methods of excellent modified polyvinyl resin molded foam goods of hardness and shock resistance that are used to obtain.In the method, with the noncrosslinking linear low density polyethylene base of 100 weight parts resin particle, 5-300 parts by weight of ethylene base aromatic monomer and with respect to 100 parts by weight of ethylene base aromatic monomers, be distributed in the aqueous medium for the polymerization starter of 1-3 weight part.Then, resulting suspended substance is heated to this monomer substantially not the temperature of polymerization reaction take place so that monomer is filled into the inside and the surface of polyvinyl resin particle.Subsequently, the temperature of rising suspended substance makes monomer polymerization, and the result is by the diffusing modified polyvinyl resin molded foam goods that obtain of the differential of vinylaromatic polymer in polyethylene.
In the embodiment of above-mentioned patent, it is in 122 ℃ the linear low density polyethylene base resin particle that styrene monomer is joined fusing point, and carry out polymerization (do not provide the fusing point of resin particle in the foregoing description, but the inventor inferring that from the name of product of the resin particle described in the embodiment this particle has above-mentioned fusing point) at 115 ℃.Polymerization under this temperature usually causes the graft polymerization of styrene monomer on Polyethylene Chain.As a result, though that the resin that obtains does not have is crosslinked, the graft polymerization of polystyrene on Polyethylene Chain having taken place, therefore can make good expanded molded article.Hereinafter, term " graftomer " expression contains the gel component of polystyrene, and the gel component of polystyrene then represented not contain fully in term " cross-linked polymer ".
In above-mentioned patent, with respect to 100 weight account polyethylenes, the amount of styrene monomer is the 5-300 weight part, when the styrene monomer that injects polyethylene surpasses 300 weight parts, the problem of a large amount of poly styrene polymer powder promptly can occur generating.
Carry out polymerization in the polyvinyl resin particle when obtaining resin when styrene monomer is filled into, polyethylene must be crosslinked with the shock resistance of enhanced foaming moulded products with reduce the dimensional change of expanded molded article after heating.Fill described resin and, obtain expanded molded article with volatile foaming agent subsequently the resin hot briquetting.In other words, if will make expanded molded article have the hardness of thermotolerance and Geng Gao, just must make polyethylene crosslinking.But also have a problem to be exactly owing to use linking agent to make crosslinked cost increase and production stage increase.
Therefore, phenylethene modified linear low density polyethylene base resin has been done required improvement, made it to prepare the expanded molded article with sufficient intensity, wherein styrene monomer and poly ratio can change in the scope of broad.
Summary of the invention
The purpose of this invention is to provide a kind of need not Polyethylene Chain is crosslinked, have an i.e. expanded molded article of excellent shock resistance of improved hardness and the excellent essential property that is subjected to thermal dimensional stability, also possesses polyethylene and possessed simultaneously.
The inventor has done extensive studies for achieving the above object, temperature when discovery is filled into resin and carries out polyreaction as polyethylene and the type by the controlled polymerization initiator and consumption, styrene-based monomers by selecting linear low-density polyethylene resin can obtain phenylethene modified linear low density polyethylene base resin expanded particle.The expanded particle that obtains like this can control ratio as amount by the resulting gel component of graft polymerization reaction of vinylbenzene on Polyethylene Chain, and can provide expanded molded article with gratifying physicals such as shock resistance, hardness and heat impedance.Therefore the inventor has finished the present invention.
The invention provides a kind of method for preparing phenylethene modified linear low density polyethylene base resin expanded particle, this method in turn includes the following steps:
With the styrene-based monomers of the non-crosslinked linear low density polyethylene base resin particle of 100 weight parts, 30-300 weight part and with respect to the styrene-based monomers of 100 weight parts, be distributed in the suspensoid that contains dispersion agent for the polymerization starter of 0.1-0.9 weight part;
By the above-mentioned dispersion that obtains of heating under the temperature that does not make the styrene-based monomers polymerization reaction take place substantially, styrene-based monomers is filled in the low-density polyethylene resin particle;
Be higher than (T-8) ℃ and be lower than the polyreaction first time of carrying out styrene-based monomers under the temperature of (T+1) ℃, T ℃ is the fusing point of low-density polyethylene resin particle here;
When polymerization conversion reaches 80-99.9%, add styrene-based monomers and be the polymerization starter of 0.1-0.9 weight part with respect to the styrene-based monomers of 100 weight parts, and styrene-based monomers is filled in the polyvinyl resin particle, be higher than (T-15) ℃ and be lower than the polyreaction second time of carrying out styrene-based monomers under the temperature of (T+5) ℃; Here T ℃ is the fusing point of polyvinyl resin particle; Wherein be used for for the first time and for the second time the total amount of the styrene monomer of polyreaction with respect to the low-density polyethylene resin particle of 100 weight parts for being no more than 1000 weight parts greater than 300 weight parts; And
Fill volatile foaming agent in polymerization process or after the polyreaction,
Therefore the gel component that contains graftomer that contains 2-40 weight % in the resinous principle of described expanded particle.
In addition, the present invention also provides the phenylethene modified linear low density polyethylene base resin expanded particle that contains volatile foaming agent and matrix resin, this matrix resin contains with respect to the non-crosslinked linear low density polyethylene base resinous principle of 100 weight parts for be no more than the polystyrene-based resinous principle of 1000 weight parts greater than 300 weight parts, wherein, the gel component that contains 2-40 weight % in the matrix resin, described gel component contains the graftomer of low-density polyethylene resin Composition and polystyrene-based resin Composition.
In addition, also to provide by above-mentioned phenylethene modified linear low density polyethylene base resin expanded particle being carried out the bulk density that pre-frothing obtains be the pre-expanded beads of 20-200 kilograms per cubic meter in the present invention.
In addition, also to provide by above-mentioned expanded particle being carried out the density that foaming obtains be the expanded molded article of 20-200 kilograms per cubic meter in the present invention.
Embodiment
The phenylethene modified linear low density polyethylene base resin expanded particle (hereinafter to be referred as the foamex particle) that obtains by preparation method of the present invention contains volatile foaming agent and matrix resin, and described matrix resin contains non-crosslinked linear low density polyethylene base resin Composition and polystyrene-based resin Composition.
The multipolymer of ethene and alpha-olefin can be used as non-crosslinked linear low density polyethylene base resin Composition used in the present invention (hereinafter to be referred as the polyvinyl resin component).
The example of alpha-olefin comprises: 1-butylene, 1-amylene, 1-hexene, 3,3-dimethyl-1-butylene, 4-methyl-1-pentene, 4,4-dimethyl-1-amylene and 1-octene, preferred 1-butylene and 1-hexene.
The ratio of ethene and alpha-olefin can change according to required physical properties, preferably 1: 0.01-1: in the scope of 0.1 (weight ratio).The meaning of term " low density " is meant that density is in the scope of 0.910-0.925 grams per milliliter.
In the scope that does not suppress the effect of wanting required for the present invention, can use new LDPE (film grade), high density polyethylene(HDPE), ethylene-propylene copolymer, vinyl-vinyl acetate copolymer and ethylene-acrylic acid copolymer with cross linked chain and/or side chain, and two or more combination of these polymkeric substance.
The example of polystyrene-based resin Composition comprises from such as the resulting resin Composition of following monomer: vinylbenzene, alpha-methyl styrene, Vinyl toluene and chloro-styrene.
With respect to 100 weight account polyethylene base resin Compositions, the amount of polystyrene-based resin Composition is for being no more than 1000 weight parts greater than 300 weight parts, is preferably greater than 300 weight parts and is no more than 900 weight parts.
Yet be difficult to be contained equably the foamex particle that is not less than 300 weight part polystyrene resin components by traditional method, the present invention can easily obtain above-mentioned particle by suitable manner.When polystyrene-based resin Composition total amount surpassed 1000 weight parts, the characteristic of polystyrene-based resin Composition was that snappiness and excellent oil-proofness and shock resistance almost show to come out.And, because vinylbenzene can not fully be adsorbed and polymerization alone by the polyvinyl resin composition, cause producing a large amount of polymer powders.
For example, can use hydrocarbon polymer such as propane, butane, Trimethylmethane, pentane, iso-pentane, pentamethylene and hexane or two kinds or two or morely unite use separately as volatile foaming agent.
With respect to the resin Composition (total amount of polyvinyl resin component and polystyrene-based resin Composition) of 100 weight parts formation foamex particle, the content of whipping agent is preferably the 5-10 weight part.
In the present invention, contain the gel component (gel fraction) of 2-40 weight % in the matrix resin of foamex particle, this gel component contains the graftomer of polyvinyl resin component and polystyrene-based resin Composition.Gel component is that the judgment criteria of graftomer is whether to have polystyrene in gel component.The present invention will contain 10 weight % or more the gel component of lustrex be defined as graftomer.The method that is used for measuring the gel component polystyrene content describes in an embodiment.
Gel fraction is not preferred less than 2 weight %, because the size that this moment, expanded molded article was heated changes and shock resistance does not all have enough improvement.On the other hand, gel fraction also is not preferred greater than 40 weight %, because this moment, bubble chamber film intensity was too high, the tensile property during the expanded molded article moulding is poor, causes the expanded molded article degraded appearance, and therefore, gel fraction is preferably 5-35 weight %.
Preferably, the foamex particle is sphere basically or L/D (L is the length of each particle, and D is the diameter of identical particle) is the cylindrical of 0.6-1.6, and average particle size is the 0.3-2.0 millimeter.
Particle with high ovality, for example L/D is not more than 0.6 and to be not less than 1.6 particle be not preferred, because these foamex particles are poor at the mold filling that carries out pre-frothing as foamed styrene modified resin particle and be filled into when obtaining expanded molded article in the mould.The shape of foamex particle is preferably substantially spherical to improve mold filling.
Average particle size is not preferred less than 0.3 millimeter, because the retentivity of whipping agent descends, and the density of expanded molded article is difficult to reduce.Average particle size also is inappropriate greater than 2.0 millimeters, because the mold filling variation of particle not only, and be difficult to make the expanded molded article attenuation.
The preparation method of foamex particle of the present invention below is described.
With respect to 100 weight account polyethylene base resin particles, when styrene-based monomers surpasses 300 weight parts, only to fill separately, the growing amount of poly styrene polymer powder is tending towards increasing.For the growing amount that makes polymer powder minimizes, in following two independent step, styrene-based monomers is filled in the polyvinyl resin particle.
Preferably, each the polyvinyl resin particle that is used for this method is cylindrical for 0.6-1.6 of sphere or L/D (L is the length of each particle, and D is the diameter of identical particle) basically, and average particle size is preferably the 0.2-1.5 millimeter.High ovality such as L/D are not more than 0.6 and to be not less than 1.6 polyvinyl resin particle be not preferred, because the polyvinyl resin particle is poor at the mold filling that carries out pre-frothing as foamed styrene modified resin particle and be filled into when obtaining expanded molded article in the mould.The shape of polyvinyl resin particle is preferably substantially spherical, to improve mold filling.Average particle size is not preferred less than 0.2 millimeter, because the retentivity of whipping agent descends, and the density of expanded molded article is difficult to reduce.Average particle size also is not preferred greater than 1.5 millimeters, because the mold filling variation of particle not only, and be difficult to make the expanded molded article attenuation.
As the composition of suspended substance, the example of aqueous medium comprises the blending agent of water, water and aqueous solvent (for example lower alcohol).
Dispersion agent is had no particular limits, and any conventional dispersion agent can use.Particularly, dispersion agent may for insoluble inorganics such as calcium phosphate, magnesium pyrophosphate, trisodium phosphate and magnesium oxide.
Polymerization starter can be usually a kind of as in the styrene-based monomers suspension polymerization initiator.But the gel generating rate changes with the difference of used polymerization starter.Such as, use t-butyl peroxy benzoic ether, dicumyl peroxide, t-butyl peroxy-2-ethylhexyl carbonic ether, 2,5-dimethyl-2,5-di-t-butyl peroxide hexane or the analogue of sloughing more hydrogen atom then can increase the gel growing amount.On the other hand, use t-butyl peroxy-3,5,5 Trimethylhexanoic acid ester, t-butyl peroxy acetic ester, 2,2-di-t-butyl peroxide butane or slough the analogue of less hydrogen atom then can reduce the gel growing amount.Can be used alone or unite the above-mentioned polymerization starter that uses two or more according to required gel fraction.
With respect to 100 parts by weight of styrene base monomers, the consumption of polymerization starter is preferably the 0.1-0.9 weight part, more preferably the 0.2-0.5 weight part.The consumption of polymerization starter is not preferred less than 0.1 weight part, because the polymerization smoothly of vinylbenzene this moment, polystyrene and polyethylene mix inhomogeneous in resin particle, thereby produces the number of polymers powder.The consumption of polymerization starter then can reduce the molecular mass of polystyrene-based resin greater than 0.9 weight part.
It is about 200 that the molecular mass of polystyrene-based resin Composition is preferably, 000-400, and 000 to obtain good physicals.The consumption of polymerization starter only can obtain the polystyrene of molecular mass less than above-mentioned scope during greater than 0.9 weight part.
With respect to 100 weight account polyethylene base resin particles, the consumption of styrene-based monomers in first time polyreaction is the 30-300 weight part.The consumption of styrene-based monomers is not preferred less than 30 weight parts, because this moment, styrene-based monomers can not be filled in the polyethylene equably.The consumption of styrene-based monomers also is not preferred greater than 300 weight parts, because the easier generation polymer powder of styrene-based monomers this moment.
With the dispersion that obtains be heated to styrene-based monomers substantially not the temperature of polymerization reaction take place so that styrene-based monomers is filled in the polyvinyl resin particle.
It is 30 minutes to 2 hours that styrene-based monomers is filled into the suitable time required in the polyvinyl resin particle, because if before styrene-based monomers fully is filled in the polyvinyl resin particle, carry out polyreaction, then can generate the poly styrene polymer powder.The temperature of polymerization reaction take place is not high more substantially helps accelerating filling speed more for styrene-based monomers, but the decomposition temperature of determining also should consider polymerization starter of temperature.
Styrene-based monomers the first time polyreaction at (T-8) ℃-(T+1) carry out in ℃ temperature range (the T here ℃ is the fusing point of above-mentioned polyvinyl resin particle).If polymeric reaction temperature is lower than (T-8) ℃ or is higher than (T+1) ℃, then graft polymerization reaction is insufficient.
When polymerization conversion reaches 80-99.9%, add styrene-based monomers and with respect to 100 parts by weight of styrene base monomers, be the polymerization starter of 0.1-0.9 weight part, and temperature transferred to (T-15)-(T+5) ℃ (the T here ℃ is the fusing point of polyvinyl resin particle), so that being filled into, styrene-based monomers carries out the polyreaction second time in the low-density polyethylene resin particle.Be used for for the first time and for the second time the styrene-based monomers total amount of polyreaction greater than 300 weight parts and be no more than 1000 weight parts.
Add the styrene-based monomers that surpasses 300 weight parts if reach at 80% o'clock in polymerization conversion, then styrene-based monomers is filled into fast in the polyvinyl resin particle and is reacted to carry out rapid polymerization, thereby can suppress the generation of poly styrene polymer powder.When polymerization conversion surpassed 99.9%, the filling of styrene-based monomers was very difficult, and transformation efficiency reduces, and causes being difficult to suppress the generation of powder particle.
The mixing solutions that contains styrene-based monomers and polymerization starter can add continuously or intermittently add to carry out the polyreaction second time.For preventing to generate polymer powder, styrene-based monomers is filled in the polyvinyl resin particle preferably and polyreaction is carried out basically simultaneously.It is not preferred adding fast, can cause polyreaction to take place before resin particle is filled because add fast with the keying action of relative higher polymeric reaction temperature.Extremely slow adding speed also is not preferred, because this may hinder polyreaction.For example, it is 3-5 hour to the monomeric reinforced time of 300-1000 parts by weight of styrene base.
And for the second time the polymeric polymerization temperature is preferably (T-8)-(T+1) ℃, so that graft polymerization reaction can more effectively carry out.
In polymerization process or after the polyreaction volatile foaming agent is filled in the resin particle so that obtain the foamex particle.The available present known method of the filling of whipping agent is carried out.For example can be in polymerization process by in encloses container, carrying out polyreaction and filling by volatile foaming agent is injected in the container.After polyreaction, can fill by volatile foaming agent is injected in the encloses container.In the filling process after polyreaction, polymerization container can not be an encloses container, as long as filling process is in encloses container.
The foamex particle of the present invention that so obtains can by ordinary method with the pre-frothing of foamex particle to predetermined bulk density (such as: the 20-200 kilograms per cubic meter) back is as pre-expanded beads.The measuring method of bulk density will be described in an embodiment.
In addition, make it in foaming, to be heated and fuse together by pre-expanded beads being inserted in the mould and being heated pre-expanded beads once more, thereby obtain expanded molded article.
Steam is the suitable heating medium as the heating pre-expanded beads.The density of expanded molded article is preferably the 20-200 kilograms per cubic meter.The density of expanded molded article is not preferred less than 20 kilograms per cubic meter because this moment goods insufficient strength.The density of expanded molded article also is not preferred greater than 200 kilograms per cubic meter, because do not reach the purpose that reduces weight this moment, and expanded molded article also possibly can't give full play to poly characteristic, such as elasticity.
The expanded molded article that obtains like this is tough and tensile, and shock strength is fine.And because through phenylethene modified processing, the hardness height of expanded molded article.
The ball falling impact value of expanded molded article is preferably 85 centimetres or higher.The ball falling impact value also can be used less than 85 centimetres expanded molded article, if but the ball falling impact value of expanded molded article is not less than 85 centimetres, then can be used as the wrapping material of fragile product, heavy assembly etc.More preferably 90 centimetres or higher of the ball falling impact values of expanded molded article.The measuring method of ball falling impact value will be described in an embodiment.
Expanded molded article of the present invention can be used for multiple use, is particularly suitable for as the interior material of car, inserts the energy absorption material in the snubber (bumper), the wrapping material of heavy article etc.
Embodiment
The present invention will be described below with reference to embodiment and Comparative Examples, but it should be understood that the present invention is not limited to the scope of these embodiment and Comparative Examples.The method of measuring numerical value described in embodiment and the Comparative Examples will be described below.
The mensuration of＜gel fraction 〉
In order to measure gel fraction, take by weighing a certain amount of resin particle sample and place in the narrow-necked bottle, and add 100 milliliters of toluene.Particle dissolved 24 hours in 130 ℃ of oil baths afterwards.After narrow-necked bottle takes out from oil bath, at once the mixture that obtains is filtered with 80 orders (0.12 millimeter of diameter) wire cloth, then, sample that is insoluble to boiling toluene and the wire cloth stayed on the wire cloth are all placed 1 hour to remove toluene, the weight of weighing gained solids in 130 ℃ of baking ovens.Divide rate with following formula calculated for gel:
Take by weighing about 200 microgram gained solidss and wrap in the ferromagnetic metal (production of Pyrofoil:Japan AnalyticalIndustry company) and make it mutually closely contact, then, make lysate with the cracker that is called JHP-3 type Curie point pyrolyzer (Curie Point Pyrolyzer Model JHP-3) (production of Japan Analytical Industry company).Lysate is analyzed with gas-chromatography automatic analysis system (Perkin Elmer production), and determines polystyrene content according to analytical results.Adopt the following analysis condition: cracking temperature: 590 ℃-5sets; Furnace temperature: 280 ℃; Entry needle temperature: 300 ℃; Chromatographic column: DB-5 (0.25 millimeter * 30 meters of 0.25 micron * diameters, J﹠amp; W produces); Column temperature: 50 ℃ (1 minute) → with 10 ℃/minute speed elevated temperature → 100 ℃ → with 40 ℃/minute speed elevated temperature → 320 ℃ (3.5 minutes); Carrier gas: He; Flow rate of carrier gas: 1 ml/min; Chromatographic column intake pressure: 12 pounds/square inch; Chromatographic column inlet temperature: 300 ℃; Detector temperature: 300 ℃; Detector: FID.The polystyrene resin QC254 that produces with Asahi Kasei company measures by absolute calibration curve method as standard specimen.
When polystyrene content is 10 weight % or when higher, measure in the gel component and contain graftomer rather than cross-linked polymer.
The mensuration of＜content of powder 〉
In order to measure content of powder, about 1000 gram polymeric size samples are joined the top be provided with in the polymkeric substance beaker of water outlet of 35 order wire cloths.In beaker, progressively add 6 liters of washing water, collect from the effusive liquid of water outlet.The liquid of collecting filters with glass fibre paper filter (GA-100), in 60 ℃ of baking ovens dry 3 hours then, measures the weight of dry polymer powder.The resin that remains in after the washing in the slurry sample also carries out drying, weighs.Content of powder calculates with following formula:
The mensuration of the molecular mass of polystyrene resin component in the＜resin particle 〉
Measure the average molecular mass (Mw) of polymkeric substance under the following conditions with gel permeation chromatography (GPC):
Determinator: high speed GPC device HLC-8020, Tosoh company produces
Chromatographic column: HSG-60S * 2, HSG-40H * 1, HSG-20H * 1, Sekisui FineChemicals company produces
Condition determination:
Column temperature: 40 ℃
Moving phase: tetrahydrofuran (THF) (THF)
Flow velocity: 1.0 ml/min
Sample size: 500 milliliters
Detector: RID-6A, Tosoh company produces
The mensuration of sample molecule quality: select the condition of working sample molecular mass, the molecular mass of sample is distributed, and to carry out the scope of related linear calibration curve overlapping with counting logarithm with different monodisperse polystyrene standard model molecular masses.
In the present invention, the polystyrene working curve is respectively 2.74 * 10 with the weight average molecular mass that Tosoh company produces
3, 1.91 * 10
4, 1.02 * 10
5, 3.55 * 10
5, 2.89 * 10
6, 4.48 * 10
6Six polystyrene standard samples (TSK polystyrene standard) draw.
The mensuration of＜bulk density 〉
Measure bulk density according to " thermosetting resin universal testing method " that JIS K6911:1955 describes.Specifically, weighing with the apparent density determinator freely falls into pre-expanded beads in the graduated cylinder, and the bulk density by following formula calculating particle:
The particle volume (cubic meter) of bulk density (kilograms per cubic meter)=weight (kilogram)/in graduated cylinder
The mensuration of＜expanded molded article density 〉
Measure the density of expanded molded article according to the method described in " the prefabricated sponge plastics thermal insulating material " of JIS A9511:1995 description.
The mensuration of＜compressive strength 〉
Measure compressive strength according to the method described in the JIS A9511:1995 " prefabricated sponge plastics thermal insulating material ".In other words, be that 10 mm/min have compressed at 5% o'clock at compression speed, be the compressive strength of 50 * 50 * 50 millimeters specimen with general experimental machine Tensilon UCT-10T (production of Orientech company) size up.
The mensuration of＜shock strength 〉
Be to measure shock strength, it is 215 * 40 * 20 millimeters sample that expanded molded article is cut into size, then sample is placed a pair of anchor clamps that are installed on 155 millimeters supports.Is mid-way on the sample width from predetermined height with the steel balls right mid-way that is added in anchor clamps of heavy 321 grams, and whether observation sample is crushed.
Repeat experiment in the different heights of fall, and the crushed minimum height of fall of sample is defined as the ball falling impact value, estimate shock strength with this.Therefore, the ball falling impact value is big more, and then shock strength is strong more.
The mensuration of＜the size changing rate that is heated 〉
From mould, take out the expanded molded article of the flats that is of a size of 400 millimeters long, 300 mm wides, 16 mm thick, and in controlled thermohygrostat (being in the JIS-K7100 state of 23 ℃ of standard temperatures, relative humidity 50%), placed 24 hours under the steady temperature.Then, the center from expanded molded article cuts out the plane square plate (150 millimeters long, 150 mm wides, 16 mm thick) with parallel upper and lower surface.In the centre of plate, longitudinally draw three parallel lines respectively with horizontal direction, 50 millimeters of spaces form the sample that meets the JIS-K6767 requirement.(preceding size: L is heated to measure the size of this sample
1) afterwards, place the inner air circulating temperature to maintain in 80 ℃ the stove its level, heat and from stove, take out sample after 168 hours, under steady temperature, in controlled thermohygrostat, to place 1 hour again, (size of working sample is heated back size: L
2).Dimension measurement experimental basis JIS-K6767 before and after being heated carries out, with following formula calculated size velocity of variation:
Size changing rate (%)=(L
2-L
1) * 100/L
1
L wherein
1Be the size of sample after the expanded molded article moulding and after keeping 24 hours under 23 ℃, 50%RH condition, L
2Be expanded molded article 80 ℃ be heated 168 hours after the size of sample).
The size of sample is to derive from three the collinear mean lengths of the sample of expanded molded article in vertical direction and horizontal direction.
Measure to find size changing rate be 0.5% or littler expanded molded article have thermotolerance.
Embodiment 1
The preparation of＜polyvinyl resin particle 〉
With extrusion machine with linear low density polyethylene (ethene-hexene copolymer, melting index is 1.0 grams/10 minutes, density is 0.921 grams per milliliter, and fusing point is 126 ℃) granulate, obtain L/D and be 0.9, average particle size is the polyvinyl resin particle of 0.8 millimeter substantially spherical.In pelletization, having added with respect to the above-mentioned polyethylene of 100 weight parts is that the talcum powder of 0.5 weight part is as foaming regulator.
The preparation of＜styrene-modified polyethylene base resin particle 〉
It is in 100 liters the autoclave that 40 kg of pure water purification, 200 grams are joined internal volume as the magnesium pyrophosphate of dispersion agent, 20 gram Sodium dodecylbenzene sulfonatees, the preparation aqueous medium.In aqueous medium, and the rotating speed that changes with per minute 150 stirs with 8 kilograms of above-mentioned polyvinyl resin particle suspensions.
In autoclave, add and contain 16 kilograms of styrene monomers (being 200 weight parts) and 48 mixing solutionss that restrain as the t-butyl peroxy-2-ethylhexyl carbonic ether (TBPOEHC) (with respect to 100 parts by weight of styrene monomers, being 0.3 weight part) of polymerization starter with respect to 100 weight account polyethylenes, and under 60 ℃, kept 60 minutes, styrene monomer is filled in the polyvinyl resin.
Then, temperature is increased to 119 ℃ and carried out polyreaction 3 hours.Polymerization conversion at styrene monomer reaches after 85%, in 3 hours, add and contain the mixing solutions that 16 kilograms of styrene monomers (being 200 weight parts) and 48 restrain as the tert butyl peroxy benzoate (TBPB) (being 0.3 weight part) of polymerization starter carry out polyreaction with respect to 100 weight account polyethylenes with respect to 100 parts by weight of styrene monomers, simultaneously styrene monomer is filled into polyethylene inside.Then, temperature is increased to 140 ℃ and kept 2 hours, forces polymerization to reduce its quantity residual monomers,, take out styrene-modified polyethylene base resin particle then with the autoclave cooling.
Recording gel fraction is 7.2 weight %.The content of polystyrene is 22.2 weight % in the gel component, and the content of powder is 0.7 weight % in the polymeric size.The molecular mass of polystyrene resin composition is about 320,000.
The preparation of＜styrene-modified polyethylene base resin expanded particle and foaminess thereof and plasticity-evaluation 〉
It is in 50 liters the sealable withstand voltage twin columns mixing tank that 20 kilograms of above-mentioned styrene-modified polyethylene base resin particles and 400 gram toluene are joined internal volume.Be rotated after the mixing tank sealing, with 2800 gram butane (normal butane: Trimethylmethane=7: 3, volume ratio, in following embodiment with the butane of equal volume ratio) be pressed in the mixing tank.Then, temperature is elevated to 70 ℃ and keep and butane was filled in the particle in 4 hours.The styrene-modified polyethylene of cooling mixing device, and taking-up then base resin expanded particle.
It is 33 kilograms per cubic meter that the expanded particle that takes out from mixing tank carries out pre-frothing to bulk density with steam at once.After about 24 hours, the pre-frothing resin particle is filled in the mould, and with steam-heated cal(l)andria so that particle in pre-frothing, fuse together, thereby obtain the expanded molded article that density is 33 kilograms per cubic meter.The intensity of the expanded molded article that obtains like this is fine, and the compressive strength of demonstration is 40 a Ns/square centimeter, and the ball falling impact value is up to 85 centimetres.Size changing rate is 0.4%.
Embodiment 2
Repeat the polymerization procedure identical with embodiment 1, different is that polymeric reaction temperature changes 121 ℃ into, obtains styrene-modified polyethylene base resin particle, pre-frothing resin particle and expanded molded article.
The bulk density of pre-frothing resin particle is 33 kilograms per cubic meter, the gel fraction that records is 26.5 weight %, and the polystyrene content in the gel component is 31.9 weight %, and the content of powder is 0.8 weight % in the polymeric size, the molecular mass of polystyrene resin composition is about 310,000.
The expanded molded article intensity that obtains like this is fine, and density is shown as 33 kilograms per cubic meter, and compressive strength is 42 a Ns/square centimeter, and the ball falling impact value is up to 95 centimetres.The size changing rate that is heated is 0.3%.
Embodiment 3
Repeat the polymerization procedure identical with embodiment 1, different is that polymeric reaction temperature changes 122 ℃ into, obtains styrene-modified polyethylene base resin particle, pre-frothing resin particle and expanded molded article.
The gel fraction of measuring is 33.5 weight %, and the polystyrene content in the gel component is 20.9 weight %, and the content of powder is 0.7 weight % in the polymeric size, and the molecular mass of polystyrene resin composition is about 300,000.
The bulk density of pre-frothing resin particle is 33 kilograms per cubic meter.The expanded molded article intensity that obtains like this is fine, and density is shown as 33 kilograms per cubic meter, and compressive strength is 44 a Ns/square centimeter, and the ball falling impact value is up to 95 centimetres.The size changing rate that is heated is 0.2%.
Embodiment 4
Repeat the polymerization procedure identical with embodiment 1, different is that polymeric reaction temperature changes 123 ℃ into, obtains styrene-modified polyethylene base resin particle, pre-frothing resin particle and expanded molded article.
The gel fraction that records is 20.8 weight %, and the polystyrene content in the gel component is 22.1 weight %, and the content of powder is 0.6 weight % in the polymeric size, and the molecular mass of polystyrene resin composition is about 290,000.
The bulk density of pre-frothing resin particle is 33 kilograms per cubic meter.The expanded molded article intensity that obtains like this is fine, and density is shown as 33 kilograms per cubic meter, and compressive strength is 42 a Ns/square centimeter, and the ball falling impact value is up to 90 centimetres.The size changing rate that is heated is 0.3%.
Embodiment 5
Repeat the polymerization procedure identical with embodiment 1, different is that polymeric reaction temperature changes 125 ℃ into, obtains styrene-modified polyethylene base resin particle, pre-frothing resin particle and expanded molded article.
Recording gel fraction is 5.8 weight %, and the polystyrene content in the gel component is 34.5 weight %, and the content of powder is 0.5 weight % in the polymeric size, and the molecular mass of polystyrene resin composition is about 280,000.
The bulk density of pre-frothing resin particle is 33 kilograms per cubic meter.The expanded molded article intensity that obtains like this is fine, and density is 33 kilograms per cubic meter, and compressive strength is 40 a Ns/square centimeter, and the ball falling impact value is up to 85 centimetres.The size changing rate that is heated is 0.4%.
Embodiment 6
It is in 100 liters the autoclave that 40 kg of pure water purification, 200 grams are joined internal volume as the magnesium pyrophosphate of dispersion agent, 20 gram Sodium dodecylbenzene sulfonatees, the preparation aqueous medium.In aqueous medium, the rotating speed that changes with per minute 150 stirs with the polyvinyl resin particle suspension that obtains among 4.4 kilograms of embodiment 1.
In autoclave, add the mixing solutions that contains 13.2 kilograms of styrene monomers (being 300 weight parts) and 39.6 gram TBPOEHC (with respect to 100 parts by weight of styrene monomers, being 0.3 weight part) with respect to 100 weight account polyethylenes, under 60 ℃, kept 60 minutes then, styrene monomer is filled in the polyvinyl resin.
Then, temperature is increased to 122 ℃ and carried out polyreaction 3 hours.Polymerization conversion at styrene monomer reaches after 85%, contain 22.4 kilograms of styrene monomers (being 500 weight parts) and 67.2 mixing solutionss that restrain TBPB (being 0.3 weight part) with respect to 100 parts by weight of styrene monomers carry out polyreaction with respect to 100 weight account polyethylenes in 5 hours, adding under 122 ℃, simultaneously styrene monomer to be filled into polyethylene inside.Then, temperature is increased to 140 ℃ and kept 2 hours, forces polymerization to reduce its quantity residual monomers, with the autoclave cooling, take out the styrene-modified polyethylene resin particle then.
Recording gel fraction is 38.5 weight %.Polystyrene content is 21.3 weight % in the gel component, and the content of powder in polymeric size is 0.8 weight %.The molecular mass of polystyrene resin composition is about 300,000.
Repeating the polymerization procedure identical with embodiment 1, different be to use resulting resin particle, is the expanded molded article of 33 kilograms per cubic meter to make pre-frothing resin particle and the density that bulk density is 33 kilograms per cubic meter.The expanded molded article intensity that obtains like this is fine, and compressive strength is shown as 48 Ns/square centimeter, and the ball falling impact value is up to 85 centimetres, and the size changing rate that is heated is 0.2%.
Embodiment 7
It is to prepare aqueous medium in 100 liters the autoclave that 40 kg of pure water purification, 200 grams are joined internal volume as the magnesium pyrophosphate of dispersion agent, 20 gram Sodium dodecylbenzene sulfonatees.In aqueous medium, the rotating speed that changes with per minute 150 stirs with the polyvinyl resin particle suspension that obtains among 8.0 kilograms of embodiment 1.
In autoclave, add the mixing solutions that contains 8.0 kilograms of styrene monomers (being 100 weight parts) and 24.0 gram TBPB (with respect to 100 parts by weight of styrene monomers, being 0.3 weight part) with respect to 100 weight account polyethylenes, under 60 ℃, kept 60 minutes then, styrene monomer is filled in the polyvinyl resin.Then, elevated temperature to 119 ℃ carried out polyreaction 3 hours.Polymerization conversion at styrene monomer reaches after 85%,, simultaneously vinylbenzene is filled in the polyethylene to carry out polyreaction at 121 ℃ of mixing solutionss that adding contains 24.0 kilograms of styrene monomers (being 300 weight parts) and 27.0 gram TBPB (being 0.3 weight part) with respect to 100 parts by weight of styrene monomers with respect to 100 weight account polyethylenes in 4 hours.Then, temperature is increased to 140 ℃ and kept 2 hours, forces polymerization to reduce its quantity residual monomers,, take out styrene-modified polyethylene base resin particle then with the autoclave cooling.With with embodiment 1 in identical method obtain pre-frothing resin particle and expanded molded article successively.
Gel fraction is 7.2 weight % in the resin particle that obtains like this.Polystyrene content is 25.0 weight % in the gel component, and the content of powder is 0.5 weight % in polymeric size.The molecular mass of polystyrene resin composition is about 300,000.
The bulk density of pre-frothing resin particle is 33 kilograms per cubic meter.The expanded molded article intensity that obtains like this is fine, and density is shown as 33 kilograms per cubic meter, and compressive strength is 43 a Ns/square centimeter, and the ball falling impact value is up to 85 centimetres, and the size changing rate that is heated is 0.4%.
Embodiment 8
Repeat the polymerization procedure identical with embodiment 7, different is for the first time the temperature of polyreaction change 126 ℃ into, as the initiator of polyreaction first time, obtain styrene-modified polyethylene base resin particle, pre-frothing resin particle and expanded molded article with DCP.
Gel fraction is 3.5 weight % in the resin particle that obtains like this.Polystyrene content is 22.8 weight % in the gel component, and the content of powder is 0.5 weight % in polymeric size.The molecular mass of polystyrene resin composition is about 300,000.
The bulk density of pre-frothing resin particle is 33 kilograms per cubic meter.The expanded molded article intensity that obtains like this is fine, and density is shown as 33 kilograms per cubic meter, and compressive strength is 42 a Ns/square centimeter, and the ball falling impact value is up to 85 centimetres, and the size changing rate that is heated is 0.4%.
Embodiment 9
Repeat the polymerization procedure identical with embodiment 7, different is for the first time and for the second time the temperature of polyreaction change 123 ℃ and 112 ℃ respectively into, with t-butyl peroxy-3,5,5-tri-methyl hexanoic acid ester (TBPOTMH) obtains styrene-modified polyethylene base resin particle, pre-frothing resin particle and expanded molded article as the initiator of polyreaction second time.
Gel fraction is 3.2 weight % in the resin particle that obtains like this.Polystyrene content is 24.4 weight % in the gel component, and the content of powder is 0.5 weight % in polymeric size.The molecular mass of polystyrene resin composition is about 340,000.
The bulk density of pre-frothing resin particle is 33 kilograms per cubic meter.The expanded molded article intensity that obtains like this is fine, and density is shown as 33 kilograms per cubic meter, and compressive strength is 43 a Ns/square centimeter, and the ball falling impact value is up to 85 centimetres, and the size changing rate that is heated is 0.3%.
Embodiment 10
Repeat the polymerization procedure identical with embodiment 7, different is for the first time and for the second time the temperature of polyreaction change 123 ℃ and 130 ℃ respectively into, as the initiator of polyreaction first time, obtain styrene-modified polyethylene base resin particle, pre-frothing resin particle and expanded molded article with DCP.
Gel fraction is 3.8 weight % in the resin particle that obtains like this.Polystyrene content is 24.2 weight % in the gel component, and the content of powder is 0.6 weight % in polymeric size.The molecular weight of polystyrene resin composition is about 240,000.
The bulk density of pre-frothing resin particle is 33 kilograms per cubic meter.The expanded molded article intensity that obtains like this is fine, and density is shown as 33 kilograms per cubic meter, and compressive strength is 43 a Ns/square centimeter, and the ball falling impact value is up to 85 cubic centimetres, and the size changing rate that is heated is 0.4%.
Embodiment 11
It is in 100 liters the autoclave that 40 kg of pure water purification, 200 grams are joined internal volume as the magnesium pyrophosphate of dispersion agent, 20 gram Sodium dodecylbenzene sulfonatees, the preparation aqueous medium.In aqueous medium, the rotating speed that changes with per minute 150 stirs with the polyvinyl resin particle suspension that obtains among 8.0 kilograms of embodiment 1.
In autoclave, add the mixing solutions that contains 8.0 kilograms of styrene monomers (is 100 weight parts with respect to 100 weight account polyethylenes) and 48.0 gram TBPB (with respect to 100 parts by weight of styrene monomers, being 0.6 weight part), under 60 ℃, kept 60 minutes then, styrene monomer is filled in the polyvinyl resin.
Then, elevated temperature to 120 ℃ carried out polyreaction 3 hours.The polymerization conversion of styrene monomer reaches after 90%, contain 24.0 kilograms of styrene monomers (being 300 weight parts) and 144.0 mixing solutionss that restrain TBPB (being 0.6 weight part) with respect to 100 parts by weight of styrene monomers carry out polyreaction with respect to 100 weight account polyethylenes in 4 hours, adding under 120 ℃, simultaneously styrene monomer to be filled in the polyethylene.Then, temperature is increased to 140 ℃ and kept 2 hours, forces polymerization to reduce its quantity residual monomers, with the autoclave cooling, take out the styrene-modified polyethylene resin particle then.Obtain pre-frothing resin particle and expanded molded article successively with the method identical with embodiment 1.
Gel fraction in the resin particle that obtains like this is 19.6 weight %.Polystyrene content is 25.0 weight % in the gel component, and the content of powder is 0.7 weight % in polymeric size.The molecular mass of polystyrene resin composition is about 260,000.
Pre-frothing resin particle bulk density is 33 kilograms per cubic meter.The expanded molded article intensity that obtains like this is fine, and density is 33 kilograms per cubic meter, and compressive strength is 40 a Ns/square centimeter, and the ball falling impact value is up to 90 centimetres, and the size changing rate that is heated is 0.3%.
Embodiment 12
Repeat the polymerization procedure identical with embodiment 11, different is for the first time and for the second time the polymerization starter consumption of polyreaction be respectively 0.3 weight part, the mixing solutions of polyreaction adds after polymerization conversion reaches 95% for the second time, obtains styrene-modified polyethylene base resin particle, pre-frothing resin particle and expanded molded article.
Recording gel fraction is 18 weight %.Polystyrene content is 23.3 weight % in the gel component, and the content of powder is 0.3 weight % in polymeric size.The molecular mass of polystyrene resin composition is about 320,000.
Pre-frothing resin particle bulk density is 33 kilograms per cubic meter.The expanded molded article intensity that obtains like this is fine, and density is shown as 33 kilograms per cubic meter, and compressive strength is 46 a Ns/square centimeter, and the ball falling impact value is up to 95 centimetres, and the size changing rate that is heated is 0.2%.
Embodiment 13
It is in 100 liters the autoclave that 40 kg of pure water purification, 200 grams are joined internal volume as the magnesium pyrophosphate of dispersion agent, 20 gram Sodium dodecylbenzene sulfonatees, the preparation aqueous medium.In aqueous medium, the rotating speed that changes with per minute 150 stirs with the polyvinyl resin particle suspension that obtains among 8.0 kilograms of embodiment 1.
In autoclave, add the mixing solutions that contains 8.0 kilograms of styrene monomers (being 100 weight parts) and 19.20 gram TBPB (with respect to 100 parts by weight of styrene monomers, being 0.24 weight part) with respect to 100 weight account polyethylenes, under 60 ℃, kept 60 minutes then, styrene monomer is filled in the polyvinyl resin.Then, elevated temperature to 120 ℃ carried out polyreaction 3 hours.Polymerization conversion at styrene monomer reaches after 90%, contain 24.0 kilograms of styrene monomers (being 300 weight parts) and 57.6 mixing solutionss that restrain TBPB (being 0.24 weight part) with respect to 100 parts by weight of styrene monomers carry out polyreaction with respect to 100 weight account polyethylenes in 4 hours, adding under 120 ℃, simultaneously styrene monomer to be filled in the polyethylene.Then, temperature is increased to 140 ℃ and kept 2 hours, forces polymerization to reduce its quantity residual monomers, with the autoclave cooling, obtain the styrene-modified polyethylene resin particle then.Obtain pre-frothing resin particle and expanded molded article successively with the method identical with embodiment 1.
Gel fraction in the resin particle that obtains like this is 17.5 weight %.Polystyrene content is 24.6 weight % in the gel component, and the content of powder is 0.5 weight % in polymeric size.The molecular mass of polystyrene resin composition is about 320,000.
Pre-frothing resin particle bulk density is 33 kilograms per cubic meter.The expanded molded article intensity that obtains like this is fine, and density is shown as 33 kilograms per cubic meter, and compressive strength is 46 a Ns/square centimeter, and the ball falling impact value is up to 95 centimetres, and the size changing rate that is heated is 0.2%.
Comparative Examples 1
Repeat the polymerization procedure identical with embodiment 1, different is that polymeric reaction temperature changes 117 ℃ into, obtains styrene-modified polyethylene base resin particle, pre-frothing resin particle and expanded molded article.
The gel fraction measured value is 0.3 weight %.Polystyrene content is 26.6 weight % in the gel component, and the content of powder is 0.5 weight % in polymeric size.The molecular mass of polystyrene resin composition is about 330,000.
Pre-frothing resin particle bulk density is 33 kilograms per cubic meter.The expanded molded article density that obtains like this is 33 kilograms per cubic meter, and compressive strength is 36 a Ns/square centimeter, and the ball falling impact value is 80 centimetres, and the size changing rate that is heated is 0.8%.
Comparative Examples 2
Repeat the polymerization procedure identical with embodiment 1, different is that polymeric reaction temperature changes 130 ℃ into, adopt dicumyl peroxide (DCP) as polymerization starter, obtain styrene-modified polyethylene base resin particle, pre-frothing resin particle and expanded molded article.
Recording gel fraction is 0.8 weight %.Polystyrene content is 25.0 weight % in the gel component, and the content of powder is 0.8 weight % in polymeric size.The molecular mass of polystyrene resin composition is about 240,000.
Pre-frothing resin particle bulk density is 33 kilograms per cubic meter.The expanded molded article density that obtains like this is 33 kilograms per cubic meter, and compressive strength is 38 a Ns/square centimeter, and the ball falling impact value is 80 centimetres, and the size changing rate that is heated is 0.7%.
Comparative Examples 3
Repeat the polymerization procedure identical with embodiment 1, different is to reach at 60% o'clock in polymerization conversion to add additional styrene monomer, obtains styrene-modified polyethylene base resin particle, pre-frothing resin particle and expanded molded article.
Recording gel fraction is 5.6 weight %.Polystyrene content is 21.4 weight % in the gel component, and the content of powder is 1.6 weight % in polymeric size.The molecular mass of polystyrene resin composition is about 320,000.
Pre-frothing resin particle bulk density is 33 kilograms per cubic meter.The expanded molded article density that obtains like this is 33 kilograms per cubic meter.Because polyreaction fails to carry out smoothly, generated a large amount of poly styrene polymer powder, thereby the fusibleness of expanded particle has reduced.As a result, compressive strength is 38 a Ns/square centimeter, and the ball falling impact value is 60 centimetres, and the size changing rate that is heated is 0.8%.
Comparative Examples 4
Repeat the polymerization procedure identical with embodiment 7, different is for the first time and the second time polymeric reaction temperature change 117 ℃ and 121 ℃ respectively into, obtain styrene-modified polyethylene base resin particle, pre-frothing resin particle and expanded molded article.
Gel fraction is 1.6 weight % in the resin particle that obtains like this.Polystyrene content is 25.0 weight % in the gel component, and the content of powder is 0.5 weight % in polymeric size.The molecular mass of polystyrene resin composition is about 300,000.
Pre-frothing resin particle bulk density is 33 kilograms per cubic meter.The expanded molded article density that obtains like this is 33 kilograms per cubic meter, and compressive strength is 38 a Ns/square centimeter, and the ball falling impact value is 80 centimetres, and the size changing rate that is heated is 0.7%.
Comparative Examples 5
Repeat the polymerization procedure identical with embodiment 7, different is that polymeric reaction temperature changes 128 ℃ into, adopt the polymerization starter of DCP, obtain styrene-modified polyethylene base resin particle, pre-frothing resin particle and expanded molded article as the polyreaction first time.
Gel fraction is 1.8 weight % in the resin particle that obtains like this.Polystyrene content is 25.0 weight % in the gel component, and the content of powder is 0.6 weight % in polymeric size.The molecular mass of polystyrene resin composition is about 300,000.
Pre-frothing resin particle bulk density is 33 kilograms per cubic meter.The expanded molded article density that obtains like this is 33 kilograms per cubic meter, and compressive strength is 40 a Ns/square centimeter, and the ball falling impact value is 80 centimetres, and the size changing rate that is heated is 0.7%.
Comparative Examples 6
Repeat the polymerization procedure identical with embodiment 7, different is for the first time and for the second time polymeric reaction temperature change 123 ℃ and 110 ℃ respectively into, adopt the polymerization starter of TBPOTMH, obtain styrene-modified polyethylene base resin particle, pre-frothing resin particle and expanded molded article as the polyreaction second time.
Gel fraction is 2.6 weight % in the resin particle that obtains like this.Polystyrene content is 25.0 weight % in the gel component, and the content of powder is 0.5 weight % in polymeric size.The molecular mass of polystyrene resin composition is about 360,000.
Pre-frothing resin particle bulk density is 33 kilograms per cubic meter.The expanded molded article density that obtains like this is 33 kilograms per cubic meter, and compressive strength is 37 a Ns/square centimeter, and the ball falling impact value is 50 centimetres, and the size changing rate that is heated is 0.4%.
Comparative Examples 7
Repeat the polymerization procedure identical with embodiment 7, different is for the first time and for the second time polymeric reaction temperature change 123 ℃ and 132 ℃ respectively into, adopt the initiators for polymerization of DCP, obtain styrene-modified polyethylene base resin particle, pre-frothing resin particle and expanded molded article as the polyreaction second time.
Gel fraction is 1.8 weight % in the resin particle that obtains like this.The content of polystyrene is 24.4 weight % in the gel component, and the content of powder is 0.6 weight % in polymeric size.The molecular mass of polystyrene resin composition is about 220,000.
Pre-frothing resin particle bulk density is 33 gram/cubic meters.The expanded molded article density that obtains like this is 33 kilograms per cubic meter, and compressive strength is 40 a Ns/square centimeter, and the ball falling impact value is 80 centimetres, and the size changing rate that is heated is 0.7%.
Comparative Examples 8
It is in 100 liters the autoclave that 40 kg of pure water purification, 200 grams are joined internal volume as the magnesium pyrophosphate of dispersion agent, 20 gram Sodium dodecylbenzene sulfonatees, the preparation aqueous medium.In aqueous medium, the rotating speed that changes with per minute 150 stirs with the polyvinyl resin particle suspension that obtains among 8.0 kilograms of embodiment 1.
In autoclave, add the mixing solutions that contains 32.0 kilograms of styrene monomers (being 400 weight parts) and 96 gram TBPB (with respect to 100 parts by weight of styrene monomers, being 0.3 weight part) with respect to 100 weight account polyethylenes, under 60 ℃, kept 60 minutes then, styrene monomer is filled in the polyvinyl resin.Then, elevated temperature to 121 ℃ carried out polyreaction 5 hours.Subsequently, temperature is increased to 140 ℃ and kept 2 hours, forces polymerization to reduce its quantity residual monomers, with the autoclave cooling, obtain styrene-modified polyethylene base resin particle then.
Recording gel fraction is 1.7 weight %.The content of polystyrene is 20.6 weight % in the gel component, and the content of powder is 1.8 weight % in polymeric size.The molecular mass of polystyrene resin composition is about 320,000.
Because polymeric size contains the number of polymers powder, and polymer powder has weakened the fusibleness of expanded particle, thereby can not obtain good pre-frothing resin particle and expanded molded article.
Comparative Examples 9
Repeat the polymerization procedure identical with embodiment 11, different is for the first time and for the second time in the polyreaction consumption of polymerization starter be respectively 0.3 weight part, the mixing solutions of polyreaction adds after polymerization conversion reaches 75% for the second time, obtains styrene-modified polyethylene base resin particle, pre-frothing resin particle and expanded molded article.
Recording gel fraction is 7.2 weight %.The content of polystyrene is 22.2 weight % in the gel component.Since the excessive independent polymerization of polystyrene monomers or stay the surface of polyvinyl resin particle, thereby the polyreaction amount of powder that generates is very big, to such an extent as to the content of powder is 1.9 weight % in polymeric size.The molecular mass of polystyrene resin composition is about 320,000.
Pre-frothing resin particle bulk density is 33 kilograms per cubic meter.The expanded molded article density that obtains like this is 33 kilograms per cubic meter, and compressive strength is 45 a Ns/square centimeter.Owing to generated a large amount of poly styrene polymer powder, the fusibleness of expanded particle has reduced, and the ball falling impact value is low to moderate 40 centimetres, and the size changing rate that is heated is 0.4%.
Material rate and the polymeric reaction condition of embodiment 1-13 and comparative example 1-9 are as shown in table 1.The molecular weight of gel fraction, polystyrene content, content of powder, polystyrene resin composition, compressive strength, ball falling impact value and the size changing rate that is heated are as shown in table 2.
Table 1
| Polyethylene/polystyrene (first time and the second time) | Polymerization conversion (%) | Polymeric reaction temperature (for the first time/for the second time) (℃) | Polymerization starter (for the first time/for the second time) | The amount of initiator (for the first time/for the second time) (weight %) | ||
| Embodiment | 1 | 100/400(200+200) | 85 | 119/119 | TPOEHC/TBPB | 0.3/0.3 |
| 2 | 100/400(200+200) | 85 | 121/121 | TPOEHC/TBPB | 0.3/0.3 | |
| 3 | 100/400(200+200) | 85 | 122/122 | TPOEHC/TBPB | 0.3/0.3 | |
| 4 | 100/400(200+200) | 85 | 123/123 | TPOEHC/TBPB | 0.3/0.3 | |
| 5 | 100/400(200+200) | 85 | 125/125 | TPOEHC/TBPB | 0.3/0.3 | |
| 6 | 100/800(300+500) | 85 | 122/122 | TBPOEHC/TBPB | 0.3/0.3 | |
| 7 | 100/400(100+300) | 85 | 119/121 | TBPB/TBPB | 0.3/0.3 | |
| 8 | 100/400(100+300) | 85 | 126/121 | DCP/TBPB | 0.3/0.3 | |
| 9 | 100/400(100+300) | 85 | 123/112 | TBPB/TBPOTMH | 0.3/0.3 | |
| 10 | 100/400(100+300) | 85 | 123/130 | TBPB/DCP | 0.3/0.3 | |
| 11 | 100/400(100+300) | 90 | 120/120 | TBPB/TBPB | 0.6/0.6 | |
| 12 | 100/400(100+300) | 95 | 120/120 | TBPB/TBPB | 0.3/0.3 | |
| 13 | 100/400(100+300) | 85 | 120/120 | TBPB/TBPB | 0.24/0.24 | |
| Comparative Examples | 1 | 100/400(200+200) | 85 | 117/117 | TPOEHC/TBPB | 0.3/0.3 |
| 2 | 100/400(200+200) | 85 | 130/130 | DCP/DCP | 0.3/0.3 | |
| 3 | 100/400(200+200) | 60 | 119/119 | TPOEHC/TBPB | 0.3/0.3 | |
| 4 | 100/400(200+300) | 85 | 117/121 | TBPB/TBPB | 0.3/0.3 | |
| 5 | 100/400(200+300) | 85 | 128/121 | DCP/TBPB | 0.3/0.3 | |
| 6 | 100/400(200+300) | 85 | 123/110 | TBPB/TBPOTMH | 0.3/0.3 | |
| 7 | 100/400(200+300) | 85 | 123/132 | TBPB/DCP | 0.3/0.3 | |
| 8 | 100/400 | - | 121 | TBPB | 0.3 | |
| 9 | 100/400(200+200) | 75 | 120/120 | TBPB/TBPB | 0.3/0.3 | |
Table 2
| Gel fraction (weight %) | Polystyrene content (weight %) | Content of powder (weight %) | Molecular mass (* 10 1) | Compressive strength (ox/square centimeter) | The ball falling impact value (centimetre) | Size changing rate (%) is heated | ||
| Embodiment | 1 | 7.2 | 22.2 | 0.7 | 32 | 40 | 85 | 0.4 |
| 2 | 26.5 | 21.9 | 0.8 | 31 | 42 | 95 | 0.3 | |
| 3 | 33.5 | 20.9 | 0.7 | 30 | 44 | 95 | 0.2 | |
| 4 | 20.8 | 22.1 | 0.6 | 29 | 42 | 90 | 0.3 | |
| 5 | 5.8 | 34.5 | 0.5 | 28 | 40 | 85 | 0.4 | |
| 6 | 38.5 | 21.3 | 0.8 | 30 | 48 | 85 | 0.2 | |
| 7 | 7.2 | 25.0 | 0.5 | 30 | 43 | 85 | 0.4 | |
| 8 | 3.5 | 22.8 | 0.5 | 30 | 42 | 85 | 0.4 | |
| 9 | 3.2 | 24.4 | 0.5 | 34 | 43 | 85 | 0.3 | |
| 10 | 3.8 | 24.2 | 0.6 | 24 | 43 | 85 | 0.4 | |
| 11 | 19.6 | 25.0 | 0.7 | 26 | 40 | 90 | 0.4 | |
| 12 | 18 | 23.3 | 0.3 | 32 | 46 | 95 | 0.3 | |
| 13 | 17.5 | 24.6 | 0.5 | 32 | 46 | 95 | 0.2 | |
| Comparative Examples | 1 | 0.3 | 26.6 | 0.5 | 33 | 36 | 80 | 0.8 |
| 2 | 0.8 | 25.0 | 0.8 | 24 | 38 | 80 | 0.7 | |
| 3 | 5.6 | 21.4 | 1.6 | 32 | 38 | 60 | 0.8 | |
| 4 | 1.6 | 25.0 | 0.5 | 30 | 38 | 80 | 0.7 | |
| 5 | 1.8 | 25.0 | 0.6 | 30 | 40 | 80 | 0.7 | |
| 6 | 2.6 | 25.0 | 0.5 | 36 | 37 | 50 | 0.4 | |
| 7 | 1.8 | 24.4 | 0.6 | 22 | 40 | 80 | 0.7 | |
| 8 | 1.7 | 20.6 | 1.8 | 32 | - | - | - | |
| 9 | 7.2 | 22.2 | 1.9 | 32 | 45 | 40 | 0.4 | |
Embodiment 14
Make the polyvinyl resin particle with the method identical with embodiment 1, different linear low density polyethylene (the ethylene-butene copolymers that is to use, melting index is 0.7 gram/10 minutes, and density is 0.922 grams per milliliter, fusing point is 121 ℃) fusing point and embodiment 1 in different.
It is in 100 liters the autoclave that 40 kg of pure water purification, 200 grams are joined internal volume as the magnesium pyrophosphate of dispersion agent, 20 gram Sodium dodecylbenzene sulfonatees, the preparation aqueous medium.In aqueous medium, the rotating speed that changes with per minute 150 stirs with 8.0 kilograms of polyvinyl resin particle suspensions.
In autoclave, add the mixing solutions that contains 8.0 kilograms of styrene monomers (being 100 weight parts) and 24.0 gram TBPB (with respect to 100 parts by weight of styrene monomers, being 0.3 weight part) with respect to 100 weight account polyethylenes, under 60 ℃, kept 60 minutes then, styrene monomer is filled in the polyvinyl resin.Then, elevated temperature to 118 ℃ carried out polyreaction 3 hours.
Polymerization conversion at styrene monomer reaches after 90%, contain 24.0 kilograms of styrene monomers (being 300 weight parts) and 72.0 mixing solutionss that restrain TBPB (being 0.3 weight part) with respect to 100 parts by weight of styrene monomers carry out polyreaction with respect to 100 weight account polyethylenes in 4 hours, adding under 118 ℃, simultaneously styrene monomer to be filled in the polyethylene.Then, temperature is increased to 140 ℃ and kept 2 hours, forces polymerization to reduce its quantity residual monomers, with the autoclave cooling, obtain styrene-modified polyethylene base resin particle then.Use the method identical to obtain pre-frothing resin particle and expanded molded article subsequently with embodiment 1.
The gel fraction of the resin particle that obtains like this is 29.8 weight %.The content of polystyrene is 24.2 weight % in the gel component, and the content of powder is 0.5 weight % in polymeric size.The molecular mass of polystyrene resin composition is about 320,000.
The bulk density of pre-frothing resin particle is 33 kilograms per cubic meter.The expanded molded article intensity that obtains like this is fine, and density is 33 kilograms per cubic meter, and compressive strength is 43 a Ns/square centimeter, and the ball falling impact value is up to 90 centimetres.Size changing rate is 0.2%.
The molecular mass of material rate among the embodiment 14 and polymeric reaction condition, content of powder, gel fraction, polystyrene content, polystyrene resin composition, ball falling impact value, compressive strength and the size changing rate that is heated are as shown in table 3.
Table 3
| Polyethylene/polystyrene (first time and the second time) | 100/400(100/300) |
| Polymeric reaction temperature (for the first time/for the second time) (℃) | 118/118 |
| Polymerization conversion (%) | 90 |
| Polymerization starter (for the first time/for the second time) (weight %) | TBPB/TBPB |
| The amount of initiator (for the first time/for the second time) (weight %) | 0.3/0.3 |
| Gel fraction (%) | 29.8 |
| Polystyrene content (weight %) | 24.2 |
| Content of powder (weight %) | 0.5 |
| Molecular mass (* 10 1) | About 32 |
| The ball falling impact value (centimetre) | 90 |
| Compressive strength (ox/square centimeter) | 43 |
| Size changing rate (%) is heated | 0.2 |
As can be seen from Table 3, even polyvinyl resin fusing point difference still can obtain all good expanded molded article of shock resistance, hardness and resistance toheat.
Embodiment 15
It is in 100 liters the autoclave that 40 kg of pure water purification, 200 grams are joined internal volume as the magnesium pyrophosphate of dispersion agent, 20 gram Sodium dodecylbenzene sulfonatees, the preparation aqueous medium.In aqueous medium, the rotating speed that changes with per minute 150 stirs with gained polyvinyl resin particle suspension among 8.0 kilograms of embodiment 1.
In autoclave, add the mixing solutions that contains 3.2 kilograms of styrene monomers (being 400 weight parts) and 9.6 gram DCP (with respect to 100 parts by weight of styrene monomers, being 0.3 weight part) with respect to 100 weight account polyethylenes, under 60 ℃, kept 60 minutes then, styrene monomer is filled in the polyvinyl resin.Then, elevated temperature to 126 ℃ carried out polyreaction 3 hours.
Polymerization conversion at styrene monomer reaches after 90%, contain 28.6 kilograms of styrene monomers (being 358 weight parts), 0.2 kilogram of alpha-methyl styrene (being 2 weight parts) and 86.4 mixing solutionss that restrain TBPB (with respect to 100 parts by weight of styrene monomers, being 0.3 weight part) carry out polyreaction with respect to 100 weight account polyethylenes with respect to 100 weight account polyethylenes in 5 hours, adding under 122 ℃, simultaneously styrene monomer to be filled in the polyethylene.Then, temperature is increased to 140 ℃ and kept 2 hours, forces polymerization to reduce its quantity residual monomers, with the autoclave cooling, obtain styrene-modified polyethylene base resin particle afterwards.Use the method identical to obtain pre-frothing resin particle and expanded molded article subsequently with embodiment 1.
The gel fraction of the resin particle that obtains like this is 30.6 weight %.The content of polystyrene is 25.0 weight % in the gel component, and the content of powder is 0.8 weight % in polymeric size.The molecular mass of polystyrene resin composition is about 300,000.
The bulk density of pre-frothing resin particle is 33 kilograms per cubic meter.The expanded molded article intensity that obtains like this is fine, and density is 33 kilograms per cubic meter, and compressive strength is 42 a Ns/square centimeter, and the ball falling impact value is up to 90 centimetres.The size changing rate that is heated is 0.2%.
The molecular mass of material rate among the embodiment 15 and polymeric reaction condition, content of powder, gel fraction, polystyrene content, polystyrene resin composition, ball falling impact value, compressive strength and the size changing rate that is heated are as shown in table 4.
Table 4
| Polyethylene/polystyrene (first time and the second time) | 100/400(40/360) |
| Polymeric reaction temperature (for the first time/for the second time) (℃) | 126/122 |
| Polymerization conversion (%) | 90 |
| Polymerization starter (for the first time/for the second time) (weight %) | DCP/TBPB |
| The amount of initiator (for the first time/for the second time) (weight %) | 0.3/0.3 |
| Gel fraction (%) | 30.6 |
| Polystyrene content (weight %) | 25.0 |
| Content of powder (weight %) | 0.8 |
| Molecular mass (* 10 1) | About 30 |
| The ball falling impact value (centimetre) | 90 |
| Compressive strength (ox/square centimeter) | 42 |
| Size changing rate (%) is heated | 0.2 |
As can be seen from Table 4, promptly use the mixture of two kinds of different styrene monomers, still can obtain all good expanded molded article of shock resistance, hardness and resistance toheat.
In sum, be filled into the selection of carrying out the polymeric polymeric reaction temperature in the polyvinyl resin particle by the controlled polymerization initiator with styrene monomer, just can controlled gel fraction, satisfy the phenylethene modified linear low density polyethylene base resin expanded particle that requires such as physicalies such as shock resistance, hardness and thermotolerances.
Claims (7)
1, a kind of preparation method of phenylethene modified linear low density polyethylene base resin expanded particle, this method comprises the following steps: successively
With the styrene-based monomers of the non-crosslinked linear low density polyethylene base resin particle of 100 weight parts, 30-300 weight part and with respect to the styrene-based monomers of 100 weight parts, be distributed in the suspensoid that contains dispersion agent for the polymerization starter of 0.1-0.9 weight part;
By not heating the above-mentioned dispersion that obtains under the temperature of polymerization reaction take place substantially, styrene-based monomers is filled in the low-density polyethylene resin particle in styrene-based monomers;
Be higher than (T-8) ℃ and be lower than the polyreaction first time of carrying out styrene-based monomers under the temperature of (T+1) ℃, T ℃ is the fusing point of low-density polyethylene resin particle here;
When polymerization conversion reaches 80-99.9%, add styrene-based monomers and be the polymerization starter of 0.1-0.9 weight part with respect to the styrene-based monomers of 100 weight parts, and styrene-based monomers is filled in the low-density polyethylene resin particle, simultaneously be higher than (T-15) ℃ and be lower than the polyreaction second time of carrying out styrene-based monomers under the temperature of (T+5) ℃; Here T ℃ is the fusing point of polyvinyl resin particle; Wherein be used for for the first time and for the second time the total amount of the styrene monomer of polyreaction with respect to the low-density polyethylene resin particle of 100 weight parts for being no more than 1000 weight parts greater than 300 weight parts; And
Fill volatile foaming agent in polymerization process or after the polyreaction,
Therefore the gel component that contains graftomer that contains 2-40 weight % in the resinous principle of expanded particle.
2, the preparation method of phenylethene modified linear low density polyethylene base resin expanded particle according to claim 1, wherein, for the second time polyreaction is carried out being higher than (T-8) ℃ and being lower than in the temperature range of (T+1) ℃.
3, the resin expanded grain of phenylethene modified linear low density polyethylene base according to claim 1 in the preparation method, wherein, each linear low density polyethylene base resin particle is sphere basically, or L/D is the cylindrical of 0.6-1.6, here L is the length of particle, and D is the diameter of particle; And average particle size is the 0.2-1.5 millimeter.
4, the phenylethene modified linear low density polyethylene base resin expanded particle that makes by the described method of claim 1, this expanded particle contains volatile foaming agent and matrix resin, described matrix resin contains with respect to 100 weight part non-crosslinked linear low density polyethylene base resinous principles for greater than 300 weight parts and less than the polystyrene-based resinous principle of 1000 weight parts, wherein, described matrix resin contains the gel component of 2-40 weight %, and described gel component contains the graft copolymer of polystyrene-based resin Composition and low-density polyethylene resin Composition.
5, a kind of phenylethene modified linear low density polyethylene base resin expanded particle is characterized in that this expanded particle makes with the described method of claim 1.
6, a kind of bulk density is the pre-expanded beads of 20-200 kilograms per cubic meter, it is characterized in that, this pre-expanded beads is to make by the phenylethene modified linear low density polyethylene base resin expanded particle described in claim 4 or 5 is carried out pre-frothing.
7, a kind of density is the expanded molded article of 20-200 in gram/cubic meter, it is characterized in that, these goods make by the described pre-expanded beads of claim 6 is carried out foaming.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2003082970A JP4410479B2 (en) | 2003-03-25 | 2003-03-25 | Electromagnetic wave absorber |
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| JP082973/2003 | 2003-03-25 |
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| TWI838933B (en) * | 2022-10-28 | 2024-04-11 | 友達光電股份有限公司 | Foaming composite material and package cushioning material formed therefrom |
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| JP4859028B2 (en) * | 2006-02-20 | 2012-01-18 | 北川工業株式会社 | Electromagnetic wave prevention sheet, electromagnetic wave prevention sheet manufacturing method, and electromagnetic wave prevention structure of electronic component |
| CN103804811A (en) * | 2014-02-19 | 2014-05-21 | 北京化工大学 | Preparation method of high-melt strength polystyrene |
| JP6185872B2 (en) * | 2014-03-28 | 2017-08-23 | 積水化成品工業株式会社 | High density polyethylene resin particles, composite resin particles, expanded particles and expanded molded articles |
| CN106008841B (en) * | 2015-03-25 | 2020-03-31 | 株式会社Jsp | Composite resin particle and method for producing same |
| JP6701943B2 (en) * | 2016-05-13 | 2020-05-27 | 株式会社ジェイエスピー | Expanded composite resin particles, method for producing the same, molded composite resin foam particles |
| CN112094622B (en) * | 2020-09-27 | 2022-03-11 | 山东大学 | Titanium dioxide coated ferroferric oxide hollow microsphere composite material and preparation method and application thereof |
| CN113736185A (en) * | 2021-09-29 | 2021-12-03 | 蔚来汽车科技(安徽)有限公司 | Composition for producing a component and component produced therefrom |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01284536A (en) * | 1988-05-12 | 1989-11-15 | Kanegafuchi Chem Ind Co Ltd | Production of pre-expanded particle of modified polyethylene resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH01284536A (en) * | 1988-05-12 | 1989-11-15 | Kanegafuchi Chem Ind Co Ltd | Production of pre-expanded particle of modified polyethylene resin |
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| TWI838933B (en) * | 2022-10-28 | 2024-04-11 | 友達光電股份有限公司 | Foaming composite material and package cushioning material formed therefrom |
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