CN104144993A - 制备聚合物制品的方法及所得的制品 - Google Patents
制备聚合物制品的方法及所得的制品 Download PDFInfo
- Publication number
- CN104144993A CN104144993A CN201280070601.9A CN201280070601A CN104144993A CN 104144993 A CN104144993 A CN 104144993A CN 201280070601 A CN201280070601 A CN 201280070601A CN 104144993 A CN104144993 A CN 104144993A
- Authority
- CN
- China
- Prior art keywords
- polymers soln
- latex
- shaped device
- polymer
- compound
- 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.)
- Pending
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 94
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- 150000001875 compounds Chemical class 0.000 claims abstract description 30
- VPKDCDLSJZCGKE-UHFFFAOYSA-N carbodiimide group Chemical group N=C=N VPKDCDLSJZCGKE-UHFFFAOYSA-N 0.000 claims abstract description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 5
- 239000003002 pH adjusting agent Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 32
- 229920000126 latex Polymers 0.000 claims description 18
- 239000004816 latex Substances 0.000 claims description 18
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 13
- -1 sulphenamide Chemical compound 0.000 claims description 13
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 7
- 239000005864 Sulphur Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000011787 zinc oxide Substances 0.000 claims description 6
- XNINAOUGJUYOQX-UHFFFAOYSA-N 2-cyanobutanoic acid Chemical compound CCC(C#N)C(O)=O XNINAOUGJUYOQX-UHFFFAOYSA-N 0.000 claims description 4
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 claims description 4
- 239000003963 antioxidant agent Substances 0.000 claims description 4
- 230000003078 antioxidant effect Effects 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- 238000002203 pretreatment Methods 0.000 claims description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 claims description 2
- 238000006424 Flood reaction Methods 0.000 claims description 2
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 claims description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 claims description 2
- 239000013543 active substance Substances 0.000 claims description 2
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- KUAZQDVKQLNFPE-UHFFFAOYSA-N thiram Chemical compound CN(C)C(=S)SSC(=S)N(C)C KUAZQDVKQLNFPE-UHFFFAOYSA-N 0.000 claims description 2
- 229960002447 thiram Drugs 0.000 claims description 2
- 239000000047 product Substances 0.000 description 29
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 20
- 150000001718 carbodiimides Chemical class 0.000 description 13
- 239000000243 solution Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 11
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 239000011240 wet gel Substances 0.000 description 7
- 230000008901 benefit Effects 0.000 description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000003618 dip coating Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229920005601 base polymer Polymers 0.000 description 2
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000006208 butylation Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 230000035800 maturation Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- FDKXTQMXEQVLRF-ZHACJKMWSA-N (E)-dacarbazine Chemical compound CN(C)\N=N\c1[nH]cnc1C(N)=O FDKXTQMXEQVLRF-ZHACJKMWSA-N 0.000 description 1
- ZMFDXQTVCRGRNM-XOMXBQTJSA-N (e)-but-2-ene Chemical compound C\C=C\C.C\C=C\C ZMFDXQTVCRGRNM-XOMXBQTJSA-N 0.000 description 1
- QTKIQLNGOKOPOE-UHFFFAOYSA-N 1,1'-biphenyl;propane Chemical compound CCC.C1=CC=CC=C1C1=CC=CC=C1 QTKIQLNGOKOPOE-UHFFFAOYSA-N 0.000 description 1
- NNOZGCICXAYKLW-UHFFFAOYSA-N 1,2-bis(2-isocyanatopropan-2-yl)benzene Chemical compound O=C=NC(C)(C)C1=CC=CC=C1C(C)(C)N=C=O NNOZGCICXAYKLW-UHFFFAOYSA-N 0.000 description 1
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 description 1
- BOSWPVRACYJBSJ-UHFFFAOYSA-N 1,3-di(p-tolyl)carbodiimide Chemical compound C1=CC(C)=CC=C1N=C=NC1=CC=C(C)C=C1 BOSWPVRACYJBSJ-UHFFFAOYSA-N 0.000 description 1
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 description 1
- 239000005059 1,4-Cyclohexyldiisocyanate Substances 0.000 description 1
- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 description 1
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical compound CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- GIUBHMDTOCBOPA-UHFFFAOYSA-N 3h-1,3-benzothiazole-2-thione;zinc Chemical compound [Zn].C1=CC=C2SC(S)=NC2=C1 GIUBHMDTOCBOPA-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- LUEQTPAVVOKMIU-UHFFFAOYSA-N N=C=N.C1(=CC=CC=C1)C1=CC=CC=C1 Chemical compound N=C=N.C1(=CC=CC=C1)C1=CC=CC=C1 LUEQTPAVVOKMIU-UHFFFAOYSA-N 0.000 description 1
- HDONYZHVZVCMLR-UHFFFAOYSA-N N=C=O.N=C=O.CC1CCCCC1 Chemical compound N=C=O.N=C=O.CC1CCCCC1 HDONYZHVZVCMLR-UHFFFAOYSA-N 0.000 description 1
- AMNLVIZWJCEBLV-UHFFFAOYSA-N NCC1=C(C=CC=C1)N=C=N Chemical class NCC1=C(C=CC=C1)N=C=N AMNLVIZWJCEBLV-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000000172 allergic effect Effects 0.000 description 1
- 208000010668 atopic eczema Diseases 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- YACLQRRMGMJLJV-UHFFFAOYSA-N chloroprene Chemical compound ClC(=C)C=C YACLQRRMGMJLJV-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N ethyl acetate Substances CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000012764 mineral filler Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- DBZCLGBDBOWIAM-UHFFFAOYSA-N n'-tert-butyl-n-(2,6-dichlorophenyl)methanediimine Chemical compound CC(C)(C)N=C=NC1=C(Cl)C=CC=C1Cl DBZCLGBDBOWIAM-UHFFFAOYSA-N 0.000 description 1
- JEQPWXGHMRFTRF-UHFFFAOYSA-N n,n'-bis(2-methylpropyl)methanediimine Chemical compound CC(C)CN=C=NCC(C)C JEQPWXGHMRFTRF-UHFFFAOYSA-N 0.000 description 1
- NASVTBDJHWPMOO-UHFFFAOYSA-N n,n'-dimethylmethanediimine Chemical compound CN=C=NC NASVTBDJHWPMOO-UHFFFAOYSA-N 0.000 description 1
- NWBVGPKHJHHPTA-UHFFFAOYSA-N n,n'-dioctylmethanediimine Chemical compound CCCCCCCCN=C=NCCCCCCCC NWBVGPKHJHHPTA-UHFFFAOYSA-N 0.000 description 1
- IDVWLLCLTVBSCS-UHFFFAOYSA-N n,n'-ditert-butylmethanediimine Chemical compound CC(C)(C)N=C=NC(C)(C)C IDVWLLCLTVBSCS-UHFFFAOYSA-N 0.000 description 1
- 229920006173 natural rubber latex Polymers 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 239000000080 wetting agent 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
- C08L13/00—Compositions of rubbers containing carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D115/00—Coating compositions based on rubber derivatives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/003—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor characterised by the choice of material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
- B29C41/14—Dipping a core
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/34—Component parts, details or accessories; Auxiliary operations
- B29C41/42—Removing articles from moulds, cores or other substrates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/22—Incorporating nitrogen atoms into the molecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/02—Polymeric products of isocyanates or isothiocyanates of isocyanates or isothiocyanates only
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
- C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
-
- 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
- C08J5/02—Direct processing of dispersions, e.g. latex, to articles
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/28—Nitrogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L15/00—Compositions of rubber derivatives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D115/00—Coating compositions based on rubber derivatives
- C09D115/005—Hydrogenated nitrile rubber
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D119/00—Coating compositions based on rubbers, not provided for in groups C09D107/00 - C09D117/00
- C09D119/02—Latex
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2033/00—Use of polymers of unsaturated acids or derivatives thereof as moulding material
- B29K2033/18—Polymers of nitriles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/48—Wearing apparel
- B29L2031/4842—Outerwear
- B29L2031/4864—Gloves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/768—Protective equipment
-
- 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
- C08J2313/00—Characterised by the use of rubbers containing carboxyl groups
-
- 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
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Dispersion Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Moulding By Coating Moulds (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
制备聚合物制品的方法，包括下列步骤：通过将含碳二亚胺基团的第一化合物与含羧基基团的第二化合物混合，制备聚合物溶液；将聚合物溶液施加到成型装置，其中施加步骤要在制备聚合物溶液的2小时内发生；和固化聚合物溶液。该聚合物溶液可具有由氢氧化铵组成的PH值调节剂。
Description
发明领域
本发明涉及制备聚合物制品的方法及所得的制品，更具体地涉及用于减少制备该类制品的时间和成本的方法。
发明背景
聚合物制品可以以多种材料和多种方法制得。典型地，将液体形式的有机化合物在这样的方法中混合在一起：其中发生化合物的交联以形成固体弹性聚合物制品。已知的方法是相对耗能和耗时的，例如可包括浸涂和注塑。尤其是，已知的制备聚合物制品的方法在使化合物一起反应后有个熟化步骤，这通常会消耗几天的时间。通过硫化步骤的进一步交联会相对更慢。而且，制备聚合物制品的许多方法包括去除表面杂质的浸提步骤，此步骤也是相对耗时的。所有的这些步骤都增加了制备聚合物制品需要的成本。
人们期望提供一种制备聚合物制品的改进方法，其通过减少制备所需的时间——包括减少熟化、硫化和浸提的时间量——降低成本。还期望提供对化学变应性的易感性降低的聚合物制品。
发明概述
根据第一方面，制备聚合物制品的方法包括下列步骤：通过使含碳二亚胺基团的第一化合物与含羧基基团的第二化合物反应，制备聚合物溶液；将聚合物溶液施加到成型装置，其中所述施加步骤在制备聚合物溶液的2小时内发生；和将聚合物溶液固化。该聚合物溶液可以具有由氢氧化铵组成的PH调节剂。
从以上公开内容和以下对各种实施方式更加详细的描述，对于本领域技术人员显而易见的是本发明提供在制备聚合物制品的技术上的显著改进。在这方面，尤其重要的是本发明给予了以更低的成本提供高质量聚合物制品的可能。鉴于下面提供的详述，各种实施例的附加特征和优势将会得到更好的理解。
某些实施方式的详述
对于本领域技术人员来说也就是对于那些拥有这一技术领域的知识和经验的人来说，显而易见的是，对于本文公开的制备聚合物制品，许多用法和设计变化是可能的。下面对各种可选特征和实施方式的详细讨论将参考制备薄壁聚合物制品来说明本发明的基本原理。考虑到本公开内容的益处，适合于其他应用的其他实施例对于本领域技术人员来说将是显而易见的。
本发明涉及制备聚合物制品的方法。利用本文所述方法可以制得的聚合物制品的代表性实施例包括医疗用、手术用和/或实验室用手套以及避孕套。考虑到本公开内容的益处，其它合适的聚合物制品，对于本领域技术人员来说将是显而易见的。有利的是，通过本文所公开的方法制备的聚合物制品中可以不含交联剂如硫、氧化锌、硬脂酸和促进剂如氨基甲酸酯、噻唑、秋兰姆、硫脲、次磺酰胺、黄原酸盐、胍及其衍生物。
根据一种实施方式，制备聚合物制品的方法包括通过将含碳二亚胺基团的第一化合物与含羧基基团的第二化合物混合，制备聚合物溶液。将聚合物溶液施加到成型装置，并固化聚合物溶液。根据非常有利的特征，所述聚合物溶液可在制备聚合物溶液的2小时内施加到成型装置，大大降低了总制备时间。
如本文所用，术语“聚合物”是包含重复结构单元的大分子，可以是弹性聚合物或乳胶，所述弹性聚合物或乳胶包括均聚物、共聚物、三元共聚物和其改性，包括聚合物的混合物在内。术语聚合物溶液是至少含碳二亚胺基团的第一化合物和含羧基基团的第二化合物以及任何必要的溶剂的混合物。聚合物制品是作为本文公开的方法的结果而形成的制品，如一副手套。
带有碳二亚胺基团的第一化合物的合适的实施例包括，例如，单-、二-、三-、四-、寡或聚碳二亚胺，脂肪族的或芳香族的，以及其混合物，其具有碳二亚胺官能团-N＝C＝N-。合适的单碳二亚胺的实施例包括但不限于二环己基碳二亚胺、二异丙基碳二亚胺、二甲基碳二亚胺、二异丁基碳二亚胺、二叔丁基碳二亚胺、叔丁基异丙基碳二亚胺、二辛基碳二亚胺、二苯基碳二亚胺、N,N'-双(2-甲基苯基)碳二亚胺、1,3-二对甲苯基碳二亚胺、二-β-萘基碳二亚胺、乙基-3-(3-二甲氨基丙基)碳二亚胺、1,3-双(三甲基甲硅烷基)碳二亚胺、N-(叔丁基)-N′-(2,6-二氯苯基)碳二亚胺、N-(叔丁基)-N′-(1-(2-氯苯基)-异丙基-1-甲基乙基)碳二亚胺和N-丁基-N'-(1-(2-氯苯基)-1-甲基乙基)碳二亚胺。合适的聚碳二亚胺的实施例包括，例如，用芳香族、脂肪族或脂环族二异氰酸酯封端的聚碳二亚胺及其混合物，例如，四甲基苯二亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、4,4'-二环己基甲烷二异氰酸酯、甲苯-2,4-二异氰酸酯、甲苯-2,6-二异氰酸酯、二苯基甲烷-4,4-二异氰酸酯、1,4-亚苯基-二异氰酸酯、二环己基甲烷-4,4'-二异氰酸酯、3-异氰酸甲酯基-3,3,5-三甲基环己基异氰酸酯、1,6-己基二异氰酸酯、1,4-环己基二异氰酸酯、降冰片基二异氰酸酯、1,5-亚萘基二异氰酸酯、4,4-二苯基二甲基甲烷二异氰酸酯、1,3-亚苯基二异氰酸酯、六亚甲基二异氰酸酯、苯二亚甲基二异氰酸酯和甲基环己烷二异氰酸酯。考虑到本公开内容的益处，其它合适的碳二亚胺对于本领域技术人员来说将是非常显而易见的。
含羧基基团的第二化合物的合适的实施例包括，例如改性天然橡胶乳胶、合成聚合物诸如丙烯腈丁二烯、异戊二烯、苯乙烯、氯丁二烯、乙烯、氯乙烯和及其共聚物、掺合物和混合物。在聚合物中的羧基基团包括，例如，羧酸诸如丙-2-烯酸、2-甲基丙烯酸、2-亚甲基丁二酸、(Z)-丁烯二酸、(E)-丁烯二酸和(E)-丁-2-烯酸、或其酸酐以及丙-2-烯酸酯诸如甲基-、乙基-、丁基-、2乙基己基-和2-羟基乙基丙烯酸酯，或除了丙-2-烯酸之外的丙烯酸单体诸如丙烯酰胺和丙烯腈，或a-甲基苯乙烯，乙酸乙烯酯等。在一个实施例中，第二化合物可以是丙烯腈与2-甲基丙烯酸的三元共聚物，2-甲基丙烯酸的量相当于基础聚合物的干重的约1％至10％，优选地基础聚合物的干重的2％至7％。考虑到本公开内容的益处，其他合适的带有羧基基团的聚合物，对本领域技术人员来说将是非常显而易见的。
聚合物溶液包括具有碳二亚胺基团的第一化合物、含有羧基基团的第二化合物和水诸如软化水的混合物。根据非常有利的特征，作为pH调节剂的弱碱也可存在于聚合物溶液中。弱碱可包括，例如，氢氧化铵，其浓度按重量计占溶液总重量的约5-10％。聚合物溶液中也可包括添加剂，例如抗氧化剂如对甲苯酚和环戊二烯(BPC)的丁基化反应产物、抗臭氧剂如石蜡、矿物填料、润滑剂、除臭剂、着色剂、抗微生物剂、增稠剂、消泡剂、润湿剂、颜料如二氧化钛。
根据非常有利的特征，聚合物溶液可在温和的条件如30-40℃下在缓慢搅拌下混合小于两个小时，或小于一个小时，或者甚至小于30分钟。因此，施加聚合物溶液的步骤可以在制备聚合物溶液步骤的2小时内，1小时内，甚至30分钟内发生。该短的熟化步骤省去了大量聚合物溶液在制备地点被存储多天的必要。
一旦聚合物溶液制成并准备好施加，则将聚合物溶液施加于成型装置。术语“成型装置(former)”广义上理解为指在成标准形状的成型装置，如聚合物溶液固化前所涂布的元件，可以包括，例如，在浸涂方法中使用的成型装置。取决于期望的聚合物制品，在注塑方法中所用的模腔表面也可以作为成型装置。
对于浸涂方法，在成型装置浸入到聚合物溶液的步骤之前，预处理成型装置的步骤是需要的。该步骤包括，例如，用包含至少表面活性剂、剥离剂和离子溶液的预涂层(precoat)预处理成型装置。例如，预涂层可以包含下列的混合物：预涂第一溶液，其具有按重量计占第一溶液的8-20％的钙离子；预涂第二溶液，其具有按重量计占第二溶液的0.05-0.25％的非离子无硅酮表面活性剂；和预涂第三溶液，其按重量计具有占第三溶液的0.5-2.5％的预均化剥离剂。成型装置可具有所施加(例如，通过浸渍)，并且在110-130℃下干燥60秒或更长时间的预涂层。优选的，当聚合物溶液被施加到成型装置时成型装置的表面温度为约50-60℃。
一旦成型装置准备好，聚合物溶液就可施加到成型装置。这可以通过许多不同的方式中的一种来完成。例如，在一般环境条件下可将(任选预涂的)成型装置浸入到聚合物溶液中达有限的一段时间(5-20秒)，然后进行干燥。可在110-130℃在烘箱中干燥30-60秒。结果是，成型装置被涂布有湿凝胶。任选地，该湿凝胶可以用温和的有机酸处理，以帮助减少湿凝胶中的pH。任选地，预浸提步骤也可包括在温水中浸渍湿凝胶涂布的成型装置。润滑剂也可被施加到湿凝胶。半干燥的湿凝胶边缘可能滚下形成珠滴。珠滴可以帮助从成型装置中剥离出聚合物制品。
除了减少熟化时间，固化聚合物溶液的步骤也会减少。固化聚合物溶液产生中间固体。例如，当第一化合物为丁二烯丙烯腈弹性体乳胶时，该固化步骤就可以加速，可以在较低温度下进行，并且可以在不到20分钟内发生以形成固化的羧基丁腈(carboxylated nitrile)乳胶。更优选地，该固化步骤可以在温度为80-130℃或者甚至80-90℃下在烘箱中发生8到20分钟，或12到16分钟。
中间固体或乳胶可以经过浸提步骤来除去表面杂质。根据非常有利的特征，浸提步骤所需的时间也可以减少，因为可以没有要除去的促进剂、硫、氧化锌或其它交联剂。浸提步骤可以通过将乳胶浸入到温度为50-60℃的水中仅仅50-120秒，优选地仅仅50-70秒而发生。一旦浸提步骤完成，可将该乳胶干燥并且可从成型装置中除去所得的聚合物制品(如厚度为0.03至0.33毫米的薄壁制品，其形成手套、指套、避孕套、气球、囊袋、导管、管道、橡胶带、止血带、松紧带、隔膜、齿科橡皮障、护套等等)。任选地，由上述公开的方法所形成的产品可允许在湿度控制的室内长久放置12-24小时。
实施例1-5。使表1所列的配方在约30℃的温度下混合约60分钟，制成聚合物制品。市售的含羧基基团的化合物(ELx-A、ELx-B、ELx-C、ELx-E和ELx-F)与碳二亚胺化合物(CDI)以及氢氧化铵、抗氧化剂(对甲苯酚和环戊二烯的丁基化反应产物(BPC))和二氧化钛(TiO2)混合。聚合物溶液中每个成分的量基于100干重量份的含羧基基团的化合物列出。将软化水加入到该化合物中以产生含有15-20％固体的制剂。干净的成型装置均匀地涂布以预涂层，然后表1的各种聚合物溶液。成型装置上湿凝胶在130℃固化15分钟。固化膜从成型装置中剥离并调节24小时。
表1
MAA＝2-甲基丙烯酸
根据实施例1-5制成的膜，测定每个膜的拉伸强度(TS)，伸长率，根据ASTM D-412的300％模量和500％模量，断裂伸长率(Eb)，在甲苯中的耐溶剂性(LS-t)和在环己酮中的耐溶剂性(Ls-c)。这些测试的结果如表2所示。结果表明，羧基化合物利用碳二亚胺化合物有效交联，产生聚合物制品，所述聚合物制品具有高拉伸强度，并对非极性甲苯(<85％的线性膨胀)和极性环己酮(<123％的线性膨胀)具有良好的耐化学性。
表2
在下列中膜的线性膨胀：甲苯(LS-t)；环己酮(LS-c)。
实施例6-9：薄壁聚合物制品使用如实施例1同样的方法制成，不同的是配方中各种类型的碳二亚胺化合物(CDI)为5份/100羧基化合物，如表3所示。膜的特性如表4所示。结果表明，碳二亚胺化合物与含羧基基团的化合物有效交联，产生具有高拉伸强度的聚合物制品。与实施例1-5相比，在较高剂量的CDI下，聚合物制品对极性和非极性溶剂具有更强的化学性。
表3
Eq＝碳二亚胺当量，1摩尔碳二亚胺基团的化学配方重量。例如，CDI eq.430是指1摩尔的聚碳二亚胺聚合物链中的碳二亚胺基团的平均重量为430克。
表4
在下列中膜的线性膨胀：甲苯(LS-t)；环己酮(LS-c)。
实施例10-15：薄膜聚合物制品利用如例1同样的方法制备，不同的是配方中使用不同剂量的具有Eq.430的CDI，如表5所示。聚合物制品的特性如表6所示。结果表明，可以使用每100份羧基化合物约1至15份的CDI，产生具有不同水平的耐化学性的薄膜。数据还表明，极性溶剂通过弹性膜的穿透泄漏时间大于330分钟。
表5
表6
在下列中膜的线性膨胀：甲苯(LS-t)；环己酮(LS-c)；己烷(LS-h)；丙酮(LS-a)BT-c＝环己酮通过弹性膜的穿透时间。
表6–续
对照实施例
实施例16.弹性膜使用美国专利公开号2002/0114943 A1的实施例所采用的无促进剂和无硫配方制备，如表7所示。氧化锌(ZnO)被用于交联羧基乳胶。氢氧化钾(KOH)溶液是用来调节化合物pH至约9.5。
实施例17.弹性膜使用美国专利号6,451,893的实施例所采用的无锌配方制备，如表7所示。促进剂二正丁基二硫代氨基甲酸锌(ZDBC)、巯基苯并噻唑锌(ZMBT)和硫被用于交联羧基乳胶。抗氧化剂2,2'-亚甲基-双-(4-甲基-6-丁基苯酚)(MBPC)被并入。
实施例18.弹性膜使用包括促进剂、硫和氧化锌的常规配方制备，如表7所示。
实施例19.弹性膜使用WO2011/068394所采用的自交联羧基丁腈乳胶(X-NBR-SXL)制备，如表7所示。
膜的特性如表8所示。膜的物理性质很好，但膜的耐化学性要比本发明的聚合物制品实施方式的耐化学性差。环己酮通过膜的穿透泄漏时间比对照实施例明显更短。
表7
表8
在下列中膜的线性膨胀：甲苯(LS-t)；环己酮(LS-c)；BT-c＝环己酮通过弹性膜的穿透时间。
实施例20-23.弹性体手套利用如实施例11同样的配方制备，不同的是在从80到130℃的各种温度下固化15分钟。所得到的特性如表9所示。结果表明，手套有很好的物理性质和耐化学性。耐久性试验表明：在实验室实际工作条件下，CDI交联手套可以戴3个小时以上而不会被人体汗液所分解。
表9
实施例20 实施例21 实施例22 实施例23
环己酮中膜的线性膨胀(LS-c)。
耐久性＝在实际工作条件下穿戴后，手套碎裂、破裂或撕裂(尤其是在分叉处)而所消耗的时间。
实施例24-27薄膜聚合物制品利用如实施例11中同样的配方制备，不同之处是，在添加碳二亚胺到乳胶之后从1小时到168小时的贮存期的不同阶段浸渍。膜特性如表10所示。
表10
实施例24 实施例25 实施例26 实施例27
环己酮中膜的线性膨胀(LS-c)；
耐久性＝在实际工作条件下穿戴后，手套碎裂、破裂或撕裂(尤其是在分叉处)而所消耗的时间。
根据以上公开内容和对某些实施方式的详细描述，明显的是，在不脱离本发明的真实范围和精神的情况下，各种修改、添加以及其他可选实施方式都是可能的。例如，在某些实施方式中，氧化锌可与第一化合物和第二化合物组合使用，而对所得聚合物制品没有显著影响。选择并且描述所讨论的实施方式，以便提供对本发明原理及其实际应用的最佳例证说明，由此能够使本领域普通技术人员利用各种实施方式中的发明，并且进行适合于所考虑的特定用途的各种修改。当根据公平地、合法地且公正地合适的广度来解释所附权利要求书时，所有此类修改和变化都在如所附权利要求书所确定的本发明的范围内。
Claims (20)
1.制备聚合物制品的方法，组合地包括下列步骤：
通过将含碳二亚胺基团的第一化合物与含羧基基团的第二化合物混合，制备聚合物溶液；
将所述聚合物溶液施加到成型装置，其中所述施加步骤在制备所述聚合物溶液的2小时内发生；和
固化所述聚合物溶液。
2.根据权利要求1所述的方法，其中将所述聚合物溶液施加到成型装置的步骤包括将所述成型装置浸渍到所述聚合物溶液中。
3.根据权利要求1所述的方法，其中所述聚合物溶液进一步包括软化水。
4.根据权利要求1所述的方法，进一步包括用预涂层预处理所述成型装置的步骤，其中所述预涂层包括至少表面活性剂、剥离剂和离子溶液。
5.根据权利要求1所述的方法，其中制备所述聚合物溶液的步骤在不使用硫、氧化锌和/或促进剂的情况下进行。
6.根据权利要求1所述的方法，进一步包括将所述聚合物制品从所述成型装置中剥离的步骤。
7.根据权利要求1所述的方法，其中所述施加步骤在制备所述聚合物溶液步骤的1小时内发生。
8.根据权利要求7所述的方法，其中所述施加步骤在制备所述聚合物溶液步骤的30分钟内发生。
9.根据权利要求1所述的方法，其中所述固化步骤持续8到20分钟。
10.根据权利要求9所述的方法，其中所述固化步骤持续12到16分钟。
11.根据权利要求1所述的方法，其中所述固化步骤使所述聚合物溶液固化以形成固化的羧基丁腈乳胶，并且进一步包括在所述固化步骤之后浸渍所述乳胶50-120秒的步骤。
12.根据权利要求11所述的方法，其中浸渍所述乳胶的步骤在所述固化步骤之后发生50-70秒。
13.根据权利要求1所述的方法，其中所述固化步骤是在温度80-90℃下进行。
14.通过上述权利要求任一项所述的方法形成的产品。
15.从固化的羧基丁腈乳胶形成的聚合物制品，组合地包括：
含碳二亚胺基团的第一化合物，
含羧基基团的第二化合物，和
pH调节剂，由氢氧化铵组成。
16.根据权利要求15所述的聚合物制品，其中所述乳胶不含下列任何一种：包含硫、氧化锌、硬脂酸的交联剂以及促进剂。
17.根据权利要求16所述的聚合物制品，其中所述促进剂包括氨基甲酸酯、噻唑、秋兰姆、次磺酰胺、硫脲、黄原酸盐、胍或其衍生物。
18.根据权利要求15所述的聚合物制品，其中所述胶乳进一步包括至少一种颜料。
19.根据权利要求15所述的聚合物制品，其中所述胶乳进一步包括抗氧化剂和抗臭氧剂。
20.根据权利要求15所述的聚合物制品，其所述聚合物制品是厚度在0.03毫米到0.33毫米的薄壁制品。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910315360.3A CN110563976A (zh) | 2012-02-29 | 2012-02-29 | 制备聚合物制品的方法及所得的制品 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/MY2012/000039 WO2013129905A1 (en) | 2012-02-29 | 2012-02-29 | Method of making a polymer article and resulting article |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910315360.3A Division CN110563976A (zh) | 2012-02-29 | 2012-02-29 | 制备聚合物制品的方法及所得的制品 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104144993A true CN104144993A (zh) | 2014-11-12 |
Family
ID=45952600
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910315360.3A Pending CN110563976A (zh) | 2012-02-29 | 2012-02-29 | 制备聚合物制品的方法及所得的制品 |
| CN201280070601.9A Pending CN104144993A (zh) | 2012-02-29 | 2012-02-29 | 制备聚合物制品的方法及所得的制品 |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910315360.3A Pending CN110563976A (zh) | 2012-02-29 | 2012-02-29 | 制备聚合物制品的方法及所得的制品 |
Country Status (22)
| Country | Link |
|---|---|
| US (1) | US11230629B2 (zh) |
| EP (1) | EP2820095B1 (zh) |
| JP (1) | JP2015513486A (zh) |
| KR (1) | KR101890211B1 (zh) |
| CN (2) | CN110563976A (zh) |
| AR (1) | AR090180A1 (zh) |
| AU (1) | AU2012371722B2 (zh) |
| BR (1) | BR112014021351B1 (zh) |
| CA (1) | CA2864708C (zh) |
| DK (1) | DK2820095T3 (zh) |
| ES (1) | ES2617502T3 (zh) |
| GB (1) | GB2514513B (zh) |
| HK (3) | HK1203992A1 (zh) |
| IN (1) | IN2014DN07448A (zh) |
| PL (1) | PL2820095T3 (zh) |
| PT (1) | PT2820095T (zh) |
| RU (1) | RU2599761C2 (zh) |
| SA (1) | SA113340326B1 (zh) |
| SG (1) | SG11201405307UA (zh) |
| TW (1) | TWI581935B (zh) |
| WO (1) | WO2013129905A1 (zh) |
| ZA (1) | ZA201406472B (zh) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI640561B (zh) * | 2016-12-19 | 2018-11-11 | 日商綠安全股份有限公司 | 手套用浸漬組成物、手套的製造方法及手套 |
| CN109310169A (zh) * | 2016-06-16 | 2019-02-05 | 绿安全股份有限公司 | 手套的制造方法、手套、以及手套用乳液组合物 |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2012371722B2 (en) * | 2012-02-29 | 2016-07-14 | Nobel Scientific Sdn. Bhd. | Method of making a polymer article and resulting article |
| JP6637223B2 (ja) * | 2017-09-08 | 2020-01-29 | 松本油脂製薬株式会社 | 強化繊維用サイジング剤及びその利用 |
| EP3816222B1 (en) | 2018-06-27 | 2023-08-23 | Midori Anzen Co., Ltd. | Dip molding composition, method for manufacturing glove, and glove |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0121083A1 (en) * | 1983-02-24 | 1984-10-10 | Union Carbide Corporation | Low-temperature crosslinking of water-borne resins |
| CN1364180A (zh) * | 1999-05-28 | 2002-08-14 | 株式会社铃木拉特克斯 | 非粘性胶乳制品 |
| US20020114943A1 (en) * | 2000-12-21 | 2002-08-22 | Derek Warneke | Elastomeric articles made from a synthetic polymer |
| EP1275681A1 (en) * | 2000-04-20 | 2003-01-15 | Teijin Limited | Polyimide film and process for producing the same |
| CN1954000A (zh) * | 2004-04-13 | 2007-04-25 | 诺瓦塞尔有限公司 | 压敏胶黏膜及其制备方法 |
| WO2011068394A1 (en) * | 2009-12-01 | 2011-06-09 | Kossan Sdn Bhd | Elastomeric rubber and rubber products without the use of vulcanizing accelerators and sulfur |
Family Cites Families (33)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3639353A (en) * | 1970-03-20 | 1972-02-01 | Goodrich Co B F | Polymers crosslinked with polycarbodiimides |
| JPS61146802A (ja) * | 1984-12-21 | 1986-07-04 | ダイヤゴム株式会社 | 透湿性且つ耐油性作業用手袋およびその製造方法 |
| US5126235A (en) | 1989-03-22 | 1992-06-30 | Fuji Photo Film Co., Ltd. | Full color recording material and a method of forming colored images |
| JPH05315838A (ja) | 1992-05-08 | 1993-11-26 | Seiko Electronic Components Ltd | 水晶発振器 |
| JP3470464B2 (ja) | 1994-07-15 | 2003-11-25 | Ｊｓｒ株式会社 | 熱硬化性樹脂組成物 |
| US6031042A (en) * | 1996-06-20 | 2000-02-29 | North Safety Products Inc. | Soft nitrile rubber formulation |
| US5798175A (en) * | 1997-01-31 | 1998-08-25 | American Tape Company | Pressure sensitive adhesives and tape product prepared therefrom |
| JP3461267B2 (ja) * | 1997-08-11 | 2003-10-27 | 大日精化工業株式会社 | ポリカルボジイミド化合物、その製造方法、樹脂組成物及び物品の処理方法 |
| US6020427A (en) * | 1997-12-10 | 2000-02-01 | Advanced Elastomer Systems, L.P. | Thermoplastic vulcanizates of carboxylated nitrile rubber and polyester thermoplastics |
| US6021524A (en) * | 1997-12-31 | 2000-02-08 | The University Of Akron | Cut resistant polymeric films |
| US5997969A (en) * | 1998-08-27 | 1999-12-07 | Gardon; John L. | Non-allergenic medical and health care devices made from crosslinked synthetic elastomers |
| DE10000656A1 (de) * | 2000-01-11 | 2001-07-12 | Basf Ag | Carbodiimide mit Carboxyl- oder Carboxylatgruppen |
| US8076445B2 (en) * | 2000-01-11 | 2011-12-13 | Robert Shane Porzio | Oligocarbodiimides for the formation of crosslinked latex films |
| US6451893B1 (en) | 2001-05-22 | 2002-09-17 | Microflex Corporation | Soft nitrile zinc oxide free medical gloves |
| US6706816B2 (en) * | 2001-07-11 | 2004-03-16 | Best Manufacturing Company | Accelerator free latex formulations, methods of making same and articles made from same |
| CA2357089A1 (en) * | 2001-09-07 | 2003-03-07 | Bayer Inc. | Elastomeric compositions |
| US6709758B2 (en) * | 2001-11-09 | 2004-03-23 | Lord Corporation | Room temperature curable X-HNBR coating |
| JP4514191B2 (ja) * | 2002-03-08 | 2010-07-28 | ロード コーポレーション | エラストマー基材用フレキシブル塗料 |
| US6777026B2 (en) * | 2002-10-07 | 2004-08-17 | Lord Corporation | Flexible emissive coatings for elastomer substrates |
| JP2003268050A (ja) * | 2002-03-19 | 2003-09-25 | Nippon Zeon Co Ltd | ディップ成形用ラテックスおよびディップ成形品 |
| US20040132886A1 (en) | 2003-01-06 | 2004-07-08 | Jian Tao | Accelerator free nitrile gloves |
| WO2004081056A2 (en) | 2003-03-14 | 2004-09-23 | Sartomer Technology Co., Inc. | Controlled release polymeric gels |
| JP2005200559A (ja) * | 2004-01-16 | 2005-07-28 | Nippon A & L Kk | ディップ成形用ラテックス、ディップ成形用組成物及びディップ成形物 |
| US20060057320A1 (en) * | 2004-09-10 | 2006-03-16 | At Tech, Inc. | Accelerator-free carboxylated latex compositions and articles |
| CA2490046A1 (en) | 2004-12-10 | 2006-06-10 | Lanxess Inc. | Multistage process for the manufacture of peroxide-cured hxnbr-polyamide thermoplastic vulcanizates |
| US20060140994A1 (en) | 2004-12-27 | 2006-06-29 | Bagwell Alison S | Application of an antimicrobial agent on an elastomeric article |
| US20090105424A1 (en) * | 2005-05-20 | 2009-04-23 | Zeon Corporation | DIP Forming Latex Composition and DIP Formed Article |
| JP5222004B2 (ja) * | 2007-04-09 | 2013-06-26 | 株式会社ブリヂストン | 封止膜及びこれを用いた太陽電池 |
| GB2455409A (en) | 2007-12-07 | 2009-06-10 | Bangkok Synthetics Co Ltd | Crosslinking of diene-type polymers |
| US20090246393A1 (en) | 2008-03-27 | 2009-10-01 | Ppg Industries Ohio, Inc. | Polycarbodiimides |
| JP5315838B2 (ja) | 2008-07-31 | 2013-10-16 | 日本ゼオン株式会社 | 接着剤組成物、複合体及び自動車用部材 |
| EP2292687B1 (en) * | 2009-09-03 | 2012-07-25 | Rhein Chemie Rheinau GmbH | Improved vulcanisable guanidine-free mixtures containing ethylene acrylate (AEM), polyacrylate (ACM) and/or hydrogenated acrylnitrile (HNBR)-based rubbers compounds, vulcanisates, prepared by cross-linking this vulcanisable mixtures and their use |
| AU2012371722B2 (en) * | 2012-02-29 | 2016-07-14 | Nobel Scientific Sdn. Bhd. | Method of making a polymer article and resulting article |
-
2012
- 2012-02-29 AU AU2012371722A patent/AU2012371722B2/en active Active
- 2012-02-29 CN CN201910315360.3A patent/CN110563976A/zh active Pending
- 2012-02-29 KR KR1020147026198A patent/KR101890211B1/ko active IP Right Grant
- 2012-02-29 SG SG11201405307UA patent/SG11201405307UA/en unknown
- 2012-02-29 ES ES12713802.2T patent/ES2617502T3/es active Active
- 2012-02-29 WO PCT/MY2012/000039 patent/WO2013129905A1/en active Application Filing
- 2012-02-29 CA CA2864708A patent/CA2864708C/en active Active
- 2012-02-29 DK DK12713802.2T patent/DK2820095T3/en active
- 2012-02-29 RU RU2014138136/05A patent/RU2599761C2/ru active
- 2012-02-29 CN CN201280070601.9A patent/CN104144993A/zh active Pending
- 2012-02-29 PL PL12713802T patent/PL2820095T3/pl unknown
- 2012-02-29 IN IN7448DEN2014 patent/IN2014DN07448A/en unknown
- 2012-02-29 PT PT127138022T patent/PT2820095T/pt unknown
- 2012-02-29 JP JP2014559850A patent/JP2015513486A/ja active Pending
- 2012-02-29 EP EP12713802.2A patent/EP2820095B1/en active Active
- 2012-02-29 GB GB1416341.4A patent/GB2514513B/en active Active
- 2012-02-29 US US14/379,355 patent/US11230629B2/en active Active
- 2012-02-29 BR BR112014021351-8A patent/BR112014021351B1/pt active IP Right Grant
-
2013
- 2013-02-24 SA SA113340326A patent/SA113340326B1/ar unknown
- 2013-02-27 AR ARP130100614A patent/AR090180A1/es active IP Right Grant
- 2013-02-27 TW TW102107098A patent/TWI581935B/zh active
-
2014
- 2014-09-03 ZA ZA2014/06472A patent/ZA201406472B/en unknown
-
2015
- 2015-05-07 HK HK15104345.7A patent/HK1203992A1/zh unknown
- 2015-05-08 HK HK15104378.7A patent/HK1203993A1/zh unknown
- 2015-05-12 HK HK15104504.4A patent/HK1203996A1/zh unknown
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0121083A1 (en) * | 1983-02-24 | 1984-10-10 | Union Carbide Corporation | Low-temperature crosslinking of water-borne resins |
| CN1364180A (zh) * | 1999-05-28 | 2002-08-14 | 株式会社铃木拉特克斯 | 非粘性胶乳制品 |
| EP1275681A1 (en) * | 2000-04-20 | 2003-01-15 | Teijin Limited | Polyimide film and process for producing the same |
| US20020114943A1 (en) * | 2000-12-21 | 2002-08-22 | Derek Warneke | Elastomeric articles made from a synthetic polymer |
| CN1954000A (zh) * | 2004-04-13 | 2007-04-25 | 诺瓦塞尔有限公司 | 压敏胶黏膜及其制备方法 |
| WO2011068394A1 (en) * | 2009-12-01 | 2011-06-09 | Kossan Sdn Bhd | Elastomeric rubber and rubber products without the use of vulcanizing accelerators and sulfur |
Non-Patent Citations (1)
| Title |
|---|
| 王箴: "<<化工辞典>>", 30 April 1985, article "羧基橡胶", pages: 662 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109310169A (zh) * | 2016-06-16 | 2019-02-05 | 绿安全股份有限公司 | 手套的制造方法、手套、以及手套用乳液组合物 |
| TWI640561B (zh) * | 2016-12-19 | 2018-11-11 | 日商綠安全股份有限公司 | 手套用浸漬組成物、手套的製造方法及手套 |
| CN109561742A (zh) * | 2016-12-19 | 2019-04-02 | 绿安全股份有限公司 | 手套用浸渍组合物、手套的制造方法和手套 |
Also Published As
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104144993A (zh) | 制备聚合物制品的方法及所得的制品 | |
| JP6802273B2 (ja) | 手袋の製造方法、手袋、及び手袋用エマルション組成物 | |
| CN103429107A (zh) | 不使用硫化助剂和硫的无尘室用弹性体橡胶手套 | |
| CN101243129A (zh) | 胶乳促进剂组合物 | |
| US20180371215A1 (en) | Aqueous resin composition and glove | |
| WO2016207352A1 (de) | Mit amin vernetzbare kautschukzusammensetzung mit hellem füllstoff | |
| JP6533812B2 (ja) | ポリマー物品の作成方法及び得られる物品 | |
| CN113767127B (zh) | 羧酸改性的腈类共聚物胶乳 | |
| JP2020189963A (ja) | エラストマー性物品 | |
| US11525046B2 (en) | Foam | |
| US20230135651A1 (en) | Method for kneading rubber | |
| US9850398B2 (en) | Powderless coating polymer and powderless glove comprising the same | |
| CN106188707A (zh) | 氯丁二烯橡胶组合物、硫化成型体及其用途 | |
| GB2582720A (en) | Method of making a polymer article and resulting article |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| REG | Reference to a national code |
Ref country code: HK Ref legal event code: DE Ref document number: 1203993 Country of ref document: HK |
|
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20141112 |
|
| RJ01 | Rejection of invention patent application after publication | ||
| REG | Reference to a national code |
Ref country code: HK Ref legal event code: WD Ref document number: 1203993 Country of ref document: HK |