CN103998515A - 偏二氯乙烯互聚物和聚(丁二酸丁二醇酯)的共混物 - Google Patents
偏二氯乙烯互聚物和聚(丁二酸丁二醇酯)的共混物 Download PDFInfo
- Publication number
- CN103998515A CN103998515A CN201280046031.XA CN201280046031A CN103998515A CN 103998515 A CN103998515 A CN 103998515A CN 201280046031 A CN201280046031 A CN 201280046031A CN 103998515 A CN103998515 A CN 103998515A
- Authority
- CN
- China
- Prior art keywords
- blend
- composition
- vdc
- interpretation
- pbs
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 97
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 title claims abstract description 64
- -1 poly(butylene succinate) Polymers 0.000 title claims abstract description 13
- 239000000178 monomer Substances 0.000 claims description 18
- 239000000654 additive Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 12
- 230000000996 additive effect Effects 0.000 claims description 10
- 239000000945 filler Substances 0.000 claims description 8
- 125000005250 alkyl acrylate group Chemical group 0.000 claims description 7
- 239000000314 lubricant Substances 0.000 claims description 7
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 claims description 6
- 239000004902 Softening Agent Substances 0.000 claims description 4
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 2
- 230000003078 antioxidant effect Effects 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 239000002516 radical scavenger Substances 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- 239000001993 wax Substances 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims 2
- 230000004888 barrier function Effects 0.000 abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 230000006866 deterioration Effects 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 229920000642 polymer Polymers 0.000 description 10
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000012856 packing Methods 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 239000004793 Polystyrene Substances 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229920001903 high density polyethylene Polymers 0.000 description 3
- 239000004700 high-density polyethylene Substances 0.000 description 3
- 229920001610 polycaprolactone Polymers 0.000 description 3
- 238000001542 size-exclusion chromatography Methods 0.000 description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000007859 condensation product Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005227 gel permeation chromatography Methods 0.000 description 2
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 2
- 235000013372 meat Nutrition 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- 229920006029 tetra-polymer Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 101000939517 Homo sapiens Ubiquitin carboxyl-terminal hydrolase 2 Proteins 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 102100029643 Ubiquitin carboxyl-terminal hydrolase 2 Human genes 0.000 description 1
- 238000000333 X-ray scattering Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 150000007520 diprotic acids Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- MYRTYDVEIRVNKP-UHFFFAOYSA-N divinylbenzene Substances C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 235000012438 extruded product Nutrition 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000000944 linseed oil Substances 0.000 description 1
- 235000021388 linseed oil Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920006344 thermoplastic copolyester Polymers 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/08—Homopolymers or copolymers of vinylidene chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/08—Homopolymers or copolymers of vinylidene chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2427/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2427/08—Homopolymers or copolymers of vinylidene chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
由包含偏二氯乙烯(VDC)互聚物和聚(丁二酸丁二醇酯)(PBS)的组合物制备的阻隔膜与在类似条件下由在所有方面类似、不同之处在于采用另外的VDC互聚物代替PBS的组合物制备的阻隔膜相比，在纵向和横向两个方向上显示出改进的抗撕强度，且在氧气传输速率上没有显著的劣化。
Description
发明背景
技术领域
本发明涉及偏二氯乙烯(VDC)互聚物(interpolymers)。在一方面，本发明涉及VDC互聚物和聚(丁二酸丁二醇酯)(PBS)的共混物，而在另一方面，本发明涉及改进的阻隔包装(barrier packaging)。
相关领域说明
偏二氯乙烯互聚物为本领域公知。VDC互聚物由于它们对大气气体和水蒸汽的质量传输的高度阻隔性而著称。通常将VDC互聚物制造成单层和多层吹制膜或流延膜。然而，由于VDC互聚物的玻璃化转变温度(Tg)与室温(23℃)接近，所以这些膜易于发生脆性破坏。同样地，在包装业中对于在由VDC互聚物制备的膜的抗撕强度上有所改进、而同时在阻隔性能(如氧气传输速率(OTR))上没有显著劣化的膜具有持续的兴趣。
USP4,725,651教导了聚合的、混溶的共混物，其包含1至80重量百分数(wt%)的VDC互聚物和20至99wt%的热塑性共聚酯树脂。共聚酯树脂由多于一种的多元醇和/或多于一种的二元酸制备得到。尽管该教导的共混物显示出的物理性质优于通过混合物的规律所预期的那些共混物的物理性质，但是共聚酯树脂对于VDC互聚物的亲和性和由该共混物制备的膜的抗撕性二者均不是完全令人满意的。
发明内容
在一种实施方式中，本发明是基本上由VDC互聚物和PBS组成的共混物。在一种实施方式中，本发明是包含VDC互聚物和PBS的组合物。由该共混物或组合物制备的膜的抗撕强度(在纵向(machine directions)和横向两个方向上)相对于在类似条件下由在所有方面类似、不同之处在于采用另外的VDC互聚物代替所述共混物或组合物的PBS的共混物或组合物制备的膜的抗撕强度有所改善。
在一种实施方式中，本发明是基本上由下列物质组成的共混物(基于所述共混物的重量)：
A.80wt%至小于100wt%的VDC互聚物；和
B.大于0wt%至20wt%的PBS。
在一种实施方式中，本发明是包含下列物质的组合物(基于所述组合物的重量)：
A.80wt%至小于100wt%的VDC互聚物；
B.大于0wt%至20wt%的PBS；和
C.至少一种添加剂或填料。
在一种实施方式中，本发明是由包含下列物质的组合物制备的膜(基于所述组合物的重量)：
A.80wt%至小于100wt%的VDC互聚物；
B.大于0wt%至20wt%的PBS；和
C.至少一种添加剂或填料。
具体实施方式
定义
本申请中的数字范围是近似值，因此除非另外说明，否则其可以包括该范围以外的值。数字范围包括以1个单位增加的从下限值到上限值的所有数值(包括下限值和上限值)，条件是在任意较低值与任意较高值之间存在至少2个单位的间隔。例如，如果组成性质、物理性质或其它性质(如分子量等)为100至1000，则明确地列举了所有的单个数值(如100、101、102等)和子区间(如100至144、155至170、197至200等)。对于包含小于1的值或者包含大于1的分数(例如1.1、1.5等)的范围，适当时将1个单位认为是0.0001、0.001、0.01或0.1。对于包含小于10(例如1至5)的个位数的范围，通常将1个单位认为是0.1。这些仅仅是具体所意指内容的实例，应认为本申请中明确说明了所列举的最低值与最高值之间的数值的所有可能组合。本申请中尤其提供了在本发明组合物中各组分的相对量、在VDC互聚物中单体单元的相对量、以及VDC互聚物和PBS的分子量的数字范围。
术语“包含”与“包括”、“含有”、“具有”或“特征在于”是同义的，其为包含端点的或端点开放的，且不排除其它未记载的要素、材料或步骤。术语“基本上由......组成”表示除了所说明的要素、材料或步骤之外，可以存在未记载的要素、材料或者步骤，其存在量并未不可接受地基本上影响主题的至少一种基本特征和新颖特性。术语“由......组成”表示仅存在所述的要素、材料或者步骤。
“共混物”、“聚合物共混物”及类似术语意指两种或更多种聚合物的组合物。该共混物可以是或可以不是混溶的。该共混物可以是或可以不是相分离的。该共混物可以包含或可以不包含一种或多种域(domain)结构，其由透射电子能谱、光散射、x射线散射和本领域已知的任何其它方法确定。
“组合物”、“制剂”及类似术语意指两种或更多种组分的混合物或共混物。在由其制备阻隔包装(如膜)的材料的混合物或共混物的上下文中，组合物包括本发明的共混物和任何其它的添加剂、填料等。
“膜”指片材、无纺或机织织物等、或它们的组合，其具有长度尺寸和宽度尺寸，且具有两个主要的表面，在两个主要表面之间具有厚度。膜可以是单层膜(仅具有一层)或多层膜(具有两层或更多层)。在大多数情况下，膜的厚度为至多约20密耳(5x10-4m)。
“层”意指形成结构的全部厚度或部分厚度的构件(member)或组件(component)，其中优选的是所述组件与所述结构基本上同延(coextensive)，且具有基本均匀的组成。
“纵向”指在制备膜的方向上的膜的长度，与“横断(transverse)向或横向”相对，所述“横断向或横向”指在通常与纵向垂直的方向上的膜的宽度。
“横断向”、“横向”和类似术语指在通常与制备膜的方向垂直的方向上的膜的宽度，与“纵向”相对，所述“纵向”指在制备膜的方向上的膜的长度。
“阻隔性(Barrier)”意指作为膜对于一种或多种气体或蒸汽(例如，氧气、水蒸汽、气味等)的渗透性测得的膜(单层或多层)的性质。“阻隔树脂”或“阻隔聚合物”意为适用于形成阻隔物的聚合物或聚合物组合物。
“聚合物”意为一种或多种单体的聚合产物，其包括均聚物以及互聚物、共聚物(copolymers)、三元共聚物、四元共聚物等以及任何前述物质的共混物和改性物，包括聚合物的嵌段、接枝、加成或缩合形式。
“链节”、“链节单元”及类似术语意为得自单个反应物分子的聚合物的部分；例如，得自乙烯的链节单元具有通式-CH2CH2-。
“互聚物”或“共聚物”指包括得自至少两种反应物(通常为单体)的链节单元的聚合物，其包括无规共聚物、嵌段共聚物、多嵌段共聚物、接枝共聚物和类似共聚物，以及三元共聚物，四元共聚物，三聚体和低聚物。
“分子量”是以道尔顿计的重均分子量(Mw)。它通过使用聚苯乙烯校正的尺寸排阻色谱法进行测量。样品制备包括在50℃使聚偏二氯乙烯树脂样品溶解于四氢呋喃(THF)中。含有超过约94%的偏二氯乙烯的树脂样品在该温度不易于溶解，在升高的温度溶解可导致聚合物分子量的降解。因此，使含有超过约94%的偏二氯乙烯的树脂样品在63℃作为1百分数(%)的溶液预溶解在经抑制的(inhibited)THF中。可以在至多83℃将样品溶解4小时而不损失分子量，但是使溶解时间和温度最小化是所期望的。然后，通过凝胶渗透色谱法(GPC)使用Polymer Laboratories软件在配有串联的两根柱的Hewlett Packard1100色谱仪上对聚合物进行分析，以测定分子量。这些柱含有可以以商品名PLGel5μMIXED-C商购自Polymer Laboratories的5μm苯乙烯/二乙烯基苯共聚物珠粒。溶剂是氮气吹洗的HPLC级THF。流速为1.0毫升/分钟，注射体积为50微升。通过使用10个窄分子量分布的聚苯乙烯标样(可以以商品名Narrow PS系列(约3000000至2000Mp)商购自PolymerLabs)连同它们的洗脱体积来推导分子量测定。
术语“抗撕强度”意为扩大带缺口的膜样品的撕裂(也称作埃尔门多夫撕裂(Elmendorf tear))所需要的力，其通过ASTM D-1922的方法测得。
偏二氯乙烯(VDC)互聚物
适用于本发明的偏二氯乙烯互聚物包含的得自偏二氯乙烯的链节单元的量典型地为至少50摩尔百分数、更典型地为至少70摩尔百分数、甚至更典型地为至少84摩尔百分数、仍然更典型地为至少90摩尔百分数。
用于本发明实施中的偏二氯乙烯互聚物还包含得自一种或多种单烯属(mono-ethylenically)不饱和单体的链节单元，所述单烯属不饱和单体与偏二氯乙烯可共聚。得自一种或多种可与偏二氯乙烯共聚的单烯属不饱和单体的链节单元的存在量典型地不多于互聚物的50摩尔百分数、更典型地不多于互聚物的25摩尔百分数、甚至更典型地不多于互聚物的16摩尔百分数、仍然更典型地不多于互聚物的10摩尔百分数。得自一种或多种与偏二氯乙烯可共聚的单烯属不饱和单体的链节单元的存在量典型地多于0摩尔百分数、更典型地多于1摩尔百分数、甚至更典型地多于2摩尔百分数、仍然更典型地多于3摩尔百分数。
适用于本发明的单烯属不饱和单体包括氯乙烯、丙烯酸烷基酯、甲基丙烯酸烷基酯、丙烯酸、甲基丙烯酸、衣康酸、丙烯腈和甲基丙烯腈。单烯属不饱和单体通常选自氯乙烯、丙烯酸烷基酯和甲基丙烯酸烷基酯，所述丙烯酸烷基酯和甲基丙烯酸烷基酯每个烷基具有1至8个碳原子。丙烯酸烷基酯和甲基丙烯酸烷基酯每个烷基通常具有1至4个碳原子。丙烯酸烷基酯和甲基丙烯酸烷基酯优选自丙烯酸甲酯、丙烯酸乙酯、和甲基丙烯酸甲酯。
用于本发明实施中的偏二氯乙烯互聚物的重均分子量(Mw)典型地为50000道尔顿至250000道尔顿、更典型地为70000道尔顿至130000道尔顿，其通过使用聚苯乙烯校正的尺寸排阻色谱法测得。
形成适用于本发明的偏二氯乙烯互聚物的方法为本领域公知。通过聚合(优选乳液聚合或悬浮聚合)来结合偏二氯乙烯单体和一种或多种单烯属不饱和单体。该方法包括至少如下所述的步骤：(a)使包含偏二氯乙烯单体的组合物和至少一种单烯属不饱和单体接触，和(b)使它们暴露于对聚合反应有效的条件下。该聚合方法在本领域的技术范围内，如USP2,968,651、3,007,903、3,879,359、6,627,679和Kirk-Othmer的"Vinylidene Chloride Monomer andPolymers"(Encyclopedia of Chemical Technology，第四版，Vol.24，John Wiley&Sons,Inc.,New York，1997，882页-923页)所教导的，应理解的是同时施用得到期望的互聚物所必需的特定的单体和单体组合物，以及具体选择的聚合条件(包括时间、温度和引发剂)，从而得到期望的分子量。该方法通常是间歇的或连续的，优选间歇的，且采用或不采用连续的或逐步的单体添加。
聚(丁二酸丁二醇酯)(PBS)
聚(丁二酸丁二醇酯)是1,4-丁二醇和丁二酸的缩合产物，或1,4-丁二醇、丁二酸和一种或多种其它二羧酸(如己二酸)的缩合产物。用于本发明实施中的PBS的重均分子量典型地为40000道尔顿至1000000道尔顿、更典型地为100000道尔顿至300000道尔顿，其通过使用聚苯乙烯校正的尺寸排阻色谱法测得。Showa High Polymer of Japan生产的BIONOLLEtm1001是可商购的PBS的实例。
VDC互聚物和PBS的共混物
本发明的共混物基本上由典型地为80wt%、更典型地为大于85wt%至小于100wt%的VDC互聚物和20wt%或更少、典型地为15wt%或更少但大于0wt%的PBS组成。共混物通常基本上由至少2wt%的PBS和不超过98wt%的VDC互聚物组成。
在一种实施方式中，使用常见的设备和共混技术将VDC互聚物和PBS彼此进行干混，以形成均匀的或基本上均匀的混合物或共混物。在另一实施方式中，使PBS溶解于偏二氯乙烯单体混合物(例如，包含偏二氯乙烯单体加上一种或多种单烯属不饱和单体和任选的一种或多种添加剂或填料的混合物)中，随后使该单体混合物经受聚合条件，以使得在包含PBS的反应物料中形成VDC互聚物。在另一实施方式中，使用常见的设备和共混技术使VDC互聚物和PBS彼此熔融共混，以形成均匀的或基本上均匀的混合物或共混物。
VDC互聚物和PBS的组合物
在一种实施方式中，本发明是包含(1)VDC互聚物、(2)PBS和(3)一种或多种添加剂和/或填料和/或其它聚合物的组合物，或换言之，本发明是含有一种或多种添加剂、填料或其它聚合物的VDC互聚物和PBS的共混物。添加剂的类型和用量取决于若干因素。一个因素是共混物的预定用途。另一因素是共混物对于添加剂的容许量(tolerance)，即在添加剂将共混物的物理性质不利地影响到不可接受的水平之前，可以将多少添加剂添加到共混物中。聚合物配制和配混领域中的那些技术人员已知其它因素。
典型的可以用于本发明实践中的添加剂包括但不限于抗氧化剂、热稳定剂(如环氧化的大豆油或亚麻籽油)、增塑剂(如柠檬酸乙酰基三丁酯、癸二酸二丁酯)、光稳定剂、颜料、加工助剂、润滑剂、除酸剂、蜡、填料等。以已知的用量和已知的方式使用这些添加剂。通常，添加剂的用量小于10wt%、更典型地小于5wt%、甚至更典型地小于3wt%，基于所述组合物的重量。
本发明的组合物可以任选地含有一种或多种为那些本领域技术人员已知的其它聚合物。聚合物的类型和用量取决于若干因素。一个这种因素是组合物的预定用途。另一因素是聚合物的相容性，即聚合物是否可以形成足够均匀的混合物，该混合物不发生预定用途所不期望的分离。其它因素对于那些本领域技术人员是显而易见的。在一种实施方式中，组合物含有至少两种根据本发明实践的偏二氯乙烯互聚物。
本发明的组合物可以用于形成多种流延制品、吹制制品、挤出制品、模塑制品、注塑制品或压延制品。由本发明的组合物制备的膜可用作包装膜和缠绕膜(wrapping films)，其可以是单层膜或多层膜。可以单独使用本发明的膜，或可以将本发明的膜层压到另一膜上或包装膜组件上，从而形成装放产品的包装。本发明的膜尤其可用于包装。氧气阻隔性在膜应用(如包装肉的初步分切块(即被运送至特定的仓库以在特定的消费者消费中用于进一步切割的大块的肉))中是重要的。包含本发明的共混物或组合物的层或膜可以任选地包含至多50wt%的至少一种其它聚合物、优选地包含至多25wt%的至少一种其它聚合物、更优选地包含至多15wt%的至少一种其它聚合物、最优选地包含至多10wt%的至少一种其它聚合物。
下列实施例进一步地说明了本发明。如无另外说明，则所有的百分数、份数和比例均基于重量。
实施例
对比例A
由基于4.8wt%的丙烯酸甲酯的树脂来制备偏二氯乙烯和丙烯酸甲酯的VDC互聚物，其组合物如表1中所报告。
表1
对比例A的组合物
a润滑剂；HDPE=高密度聚乙烯。
b润滑剂。
c润滑剂。
d增滑剂。
e抗粘连剂。
f抗氧化剂/润滑剂。
g润滑剂。
h增塑剂。
i增塑剂。
组分a-g在环境条件下是固体(23℃和大气压)，将其预混合，并且作为母炼胶加入。组分h和i在环境条件下是液体，在聚合过程期间加入。
使用1.75英寸直径的WELEXtm挤出机在表2中报告的条件下将该组合物制造成流延膜。
表2
WELEX挤出机操作条件
在埃尔门多夫撕裂测试(ASTM D1922)之前，使膜在23℃和50%相对湿度老化3周。在纵向和横断(横)向两个方向上测量了膜的抗撕强度，分别为8±1g/密耳和60±9g/密耳。根据ASTM D3985在23℃和50%相对湿度测量了膜的氧气传输速率(OTR)，其为2.4cc-密耳/(100in2)/天。
对比例B
首先将对比例A中使用的偏二氯乙烯和丙烯酸甲酯的VDC互聚物与表1的添加剂混合，随后将其与聚(己内酯)(TONE P767，得自The Dow ChemicalCompany)干混得到95wt%VDC互聚物和5wt%聚(己内酯)的混合物。随后在与对比例A中所使用的挤出条件相同的挤出条件下将该组合物挤出成流延膜。在相同的条件下使膜老化，测得的在纵向和横断向上的埃尔门多夫抗撕强度为18±1g/密耳和86±12g/密耳，OTR为9.1cc-密耳/(100in2)/天。
实施例1
重复对比例B，不同之处在于用聚(丁二酸丁二醇酯)(BIONOLLEtm1001，由Showa High Polymer生产)代替聚(己内酯)。在相同的条件下使膜老化，测得的在纵向和横断向上的埃尔门多夫抗撕强度为13±1g/密耳和74±8g/密耳，OTR为4.2cc-密耳/(100in2)/天。该实施例的埃尔门多夫抗撕强度优于对比例A中所报告的埃尔门多夫抗撕强度，尽管该实施例的埃尔门多夫抗撕强度与对比例B的埃尔门多夫抗撕强度大致相同，但是OTR为两倍好。
Claims (16)
1.一种共混物，基于共混物的重量，该共混物基本上由以下物质组成：
A.80wt%至小于100wt%的偏二氯乙烯(VDC)互聚物；和
B.大于0wt%至20wt%的聚(丁二酸丁二醇酯)(PBS)。
2.权利要求1的共混物，其包含2wt%至15wt%的PBS。
3.权利要求1的共混物，其中所述PBS的Mw为40000道尔顿至1000000道尔顿。
4.权利要求1的共混物，其中所述VDC互聚物的Mw为50000道尔顿至250000道尔顿。
5.权利要求1的共混物，其中所述VDC互聚物包含70摩尔百分数或更多的得自偏二氯乙烯单体的链节单元。
6.权利要求5的共混物，其中所述VDC互聚物包含得自以下物质的链节单元：丙烯酸烷基酯、甲基丙烯酸烷基酯或丙烯腈单体中的一种或多种。
7.权利要求6的共混物，其中所述VDC互聚物由得自偏二氯乙烯和丙烯酸甲酯单体的链节单元组成。
8.一种组合物，基于组合物的重量，所述组合物包含：
A.80wt%至小于100wt%的VDC互聚物；
B.大于0wt%至20wt%的PBS；和
C.一种或多种添加剂。
9.权利要求8的组合物，其包含2wt%至15wt%的PBS。
10.权利要求8的组合物，其中所述PBS的Mw为40000道尔顿至1000000道尔顿。
11.权利要求8的组合物，其中所述VDC互聚物的Mw为50000道尔顿至250000道尔顿。
12.权利要求8的组合物，其中所述VDC互聚物包含70摩尔百分数或更多的得自偏二氯乙烯单体的链节单元。
13.权利要求12的组合物，其中所述VDC互聚物包含得自以下物质的链节单元：丙烯酸烷基酯、甲基丙烯酸烷基酯或丙烯腈单体中的一种或多种。
14.权利要求13的组合物，其中所述VDC互聚物由得自偏二氯乙烯和丙烯酸甲酯单体的链节单元组成。
15.权利要求8的组合物，其中所述添加剂是抗氧化剂、热稳定剂、增塑剂、光稳定剂、颜料、加工助剂、润滑剂、除酸剂、填料和蜡中的一种或多种。
16.由权利要求8-15的任一项的组合物制备的膜。
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201161539263P | 2011-09-26 | 2011-09-26 | |
| US61/539,263 | 2011-09-26 | ||
| PCT/US2012/054895 WO2013048738A1 (en) | 2011-09-26 | 2012-09-12 | Vinylidene chloride interpolymer and poly(butylene succinate) blend |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103998515A true CN103998515A (zh) | 2014-08-20 |
| CN103998515B CN103998515B (zh) | 2016-08-17 |
Family
ID=46940608
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280046031.XA Active CN103998515B (zh) | 2011-09-26 | 2012-09-12 | 偏二氯乙烯互聚物和聚(丁二酸丁二醇酯)的共混物 |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US9056972B2 (zh) |
| EP (1) | EP2751200B1 (zh) |
| JP (1) | JP6030139B2 (zh) |
| CN (1) | CN103998515B (zh) |
| BR (1) | BR112014003387B1 (zh) |
| ES (1) | ES2626280T3 (zh) |
| RU (1) | RU2627388C2 (zh) |
| WO (1) | WO2013048738A1 (zh) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103998515B (zh) * | 2011-09-26 | 2016-08-17 | 陶氏环球技术有限责任公司 | 偏二氯乙烯互聚物和聚(丁二酸丁二醇酯)的共混物 |
| WO2015069418A1 (en) | 2013-11-11 | 2015-05-14 | Dow Global Technologies Llc | A process to produce a vinylidene chloride-based heteropolymer |
| US10233321B2 (en) | 2014-08-15 | 2019-03-19 | Dow Global Technologies Llc | Composition, a film made therefrom and an article including the film |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101528844A (zh) * | 2006-09-05 | 2009-09-09 | 索维公司 | 至少一种偏二氯乙烯聚合物的组合物 |
| WO2011110567A1 (en) * | 2010-03-10 | 2011-09-15 | Solvay Sa | Composition based on a vinylidene chloride copolymer |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3007903A (en) | 1956-04-16 | 1961-11-07 | Dow Chemical Co | Continuous polymerization process |
| US2968651A (en) | 1957-02-08 | 1961-01-17 | Dow Chemical Co | Process for preparing normally crystalline vinylidene chloride polymers |
| US3879359A (en) | 1972-04-11 | 1975-04-22 | Dow Chemical Co | High vinylidene chloride polymer content coating resins and method of preparation |
| US4725651A (en) | 1985-12-17 | 1988-02-16 | The Dow Chemical Company | Polymeric blend composition of a vinylidene chloride interpolymer and a thermoplastic copolyester |
| US5270390A (en) | 1990-08-22 | 1993-12-14 | Kureha Kagaku Kogyo Kabushiki Kaisha | Resin composition and heat shrinkable film comprising the same composition layer |
| EP1115764B1 (en) | 1998-08-18 | 2004-08-04 | Dow Global Technologies Inc. | Extrudable barrier polymer compositions, process for preparing the compositions and monolayer or multilayer structures comprising the compositions |
| CN103998515B (zh) * | 2011-09-26 | 2016-08-17 | 陶氏环球技术有限责任公司 | 偏二氯乙烯互聚物和聚(丁二酸丁二醇酯)的共混物 |
-
2012
- 2012-09-12 CN CN201280046031.XA patent/CN103998515B/zh active Active
- 2012-09-12 RU RU2014116960A patent/RU2627388C2/ru active
- 2012-09-12 WO PCT/US2012/054895 patent/WO2013048738A1/en active Application Filing
- 2012-09-12 EP EP12766528.9A patent/EP2751200B1/en active Active
- 2012-09-12 US US14/343,249 patent/US9056972B2/en active Active
- 2012-09-12 JP JP2014531865A patent/JP6030139B2/ja active Active
- 2012-09-12 ES ES12766528.9T patent/ES2626280T3/es active Active
- 2012-09-12 BR BR112014003387-0A patent/BR112014003387B1/pt active IP Right Grant
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101528844A (zh) * | 2006-09-05 | 2009-09-09 | 索维公司 | 至少一种偏二氯乙烯聚合物的组合物 |
| WO2011110567A1 (en) * | 2010-03-10 | 2011-09-15 | Solvay Sa | Composition based on a vinylidene chloride copolymer |
Non-Patent Citations (1)
| Title |
|---|
| JEONG-CHANG LEE,ETC: "crystallization kinetics and morphology in miscible blends of two crystalline polymers", 《POLYMER JOURNAL》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| RU2627388C2 (ru) | 2017-08-08 |
| EP2751200B1 (en) | 2017-04-12 |
| US9056972B2 (en) | 2015-06-16 |
| US20140221555A1 (en) | 2014-08-07 |
| BR112014003387A2 (pt) | 2017-03-01 |
| CN103998515B (zh) | 2016-08-17 |
| WO2013048738A1 (en) | 2013-04-04 |
| JP6030139B2 (ja) | 2016-11-24 |
| BR112014003387B1 (pt) | 2020-12-15 |
| EP2751200A1 (en) | 2014-07-09 |
| JP2014526598A (ja) | 2014-10-06 |
| RU2014116960A (ru) | 2015-11-10 |
| WO2013048738A8 (en) | 2014-06-12 |
| ES2626280T3 (es) | 2017-07-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103998515A (zh) | 偏二氯乙烯互聚物和聚(丁二酸丁二醇酯)的共混物 | |
| JPH05255560A (ja) | 塩化ビニリデン組成物及び該組成物から製造するフィルム | |
| US4518515A (en) | Moulding compositions of vinyl chloride polymers, graft polymers and polymeric plasticizers having a high resistance to ageing | |
| Wu et al. | The co-continuous morphology of biocompatible ethylene-vinyl acetate copolymers/poly (ε-caprolactone) blend: effect of viscosity ratio and vinyl acetate content | |
| CN110023401A (zh) | 苯乙烯-丁二烯共聚物（sbc）与无规嵌段和smma的共混物 | |
| CN103814065B (zh) | 在不使用共混机的情况下将添加剂混入到偏二氯乙烯聚合物中的方法 | |
| EP3105290B1 (en) | Styrene methyl methacrylate copolymers (smma) as compatibilizing agents | |
| WO2013048746A1 (en) | Batch suspension process for the manufacture of vinylidene chloride terpolymers | |
| JPS6323948A (ja) | 塩化ビニル重合体およびグラフト重合体より製造した改良された性質を有する熱可塑性成形用材料 | |
| CA2344344C (en) | Improved rubber modified monovinylidene aromatic polymer compositions | |
| US12031024B2 (en) | Thermoplastic resin composition and molded article thereby | |
| Rocha et al. | Influence of physical–chemical interactions on the thermal stability and surface properties of poly (vinyl chloride)-b-poly (hydroxypropyl acrylate)-b-poly (vinyl chloride) block copolymers | |
| Velasquez et al. | Instability of styrene/polystyrene/polybutadiene/polystyrene‐b‐polybutadiene emulsions that emulate styrene polymerization in the presence of polybutadiene | |
| KR20210028224A (ko) | 바닥재 적용을 위한 올레핀계 중합체 조성물 | |
| CN105683274A (zh) | 用于制造基于偏二氯乙烯的杂聚物的方法 | |
| US10233321B2 (en) | Composition, a film made therefrom and an article including the film | |
| Nuisin et al. | Synthesis and property behavior of dioctyl phthalate plasticized styrene–acrylate particles by Shirasu porous glass emulsification and subsequent suspension copolymerization | |
| US20230059319A1 (en) | Styrene butadiene block copolymers with low crosslinking | |
| KR101839483B1 (ko) | 열안정성이 우수한 창호재용 수지 조성물 | |
| JP2006143944A (ja) | ブロック共重合体混合物および成形品 | |
| Sehgal et al. | Structure property relationship of polymer blends: Effect of grafting on mechanical properties | |
| WO2017106128A2 (en) | Acrylic composition | |
| Filinskaya et al. | Study of the Service Properties and Biodegradability of Polymer–Colloid Protective Systems Made from Latex Blends of a Vinyl Acetate Copolymer and Elastomers | |
| Aleksandrova | Adhesives as polymer blends | |
| JPS63142007A (ja) | 重合体の製造方法 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20190923 Address after: michigan Patentee after: Escape Salan USA Co.,Ltd. Address before: michigan Patentee before: Dow Global Technologies Llc |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231010 Address after: Seoul, South Kerean Patentee after: Aiskai Zhixin Co.,Ltd. Address before: Michigan, USA Patentee before: Escape Salan USA Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231128 Address after: Southeast of the intersection of New Area 1st Road and New Area 4th Road in Xiaying Binhai Economic Development Zone, Changyi City, Weifang City, Shandong Province Patentee after: WEIFANG YAXING CHEMICAL CO.,LTD. Address before: Seoul, South Kerean Patentee before: Aiskai Zhixin Co.,Ltd. |
|
| TR01 | Transfer of patent right |