CN103069343B - 羧基酯缩酮除去组合物、其制造方法及应用 - Google Patents
羧基酯缩酮除去组合物、其制造方法及应用 Download PDFInfo
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- CN103069343B CN103069343B CN201180038383.6A CN201180038383A CN103069343B CN 103069343 B CN103069343 B CN 103069343B CN 201180038383 A CN201180038383 A CN 201180038383A CN 103069343 B CN103069343 B CN 103069343B
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- Prior art keywords
- removal composition
- alkyl
- hydrogen
- removal
- solvent
- Prior art date
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- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical class CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-M isovalerate Chemical compound CC(C)CC([O-])=O GWYFCOCPABKNJV-UHFFFAOYSA-M 0.000 description 1
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 1
- 238000005907 ketalization reaction Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 150000004730 levulinic acid derivatives Chemical class 0.000 description 1
- 235000001510 limonene Nutrition 0.000 description 1
- 229940087305 limonene Drugs 0.000 description 1
- 229930007744 linalool Natural products 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 235000010420 locust bean gum Nutrition 0.000 description 1
- 239000000711 locust bean gum Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 1
- BBEJNBLSSWFDSN-UHFFFAOYSA-N methylamino benzoate Chemical compound CNOC(=O)C1=CC=CC=C1 BBEJNBLSSWFDSN-UHFFFAOYSA-N 0.000 description 1
- QXLPXWSKPNOQLE-UHFFFAOYSA-N methylpentynol Chemical compound CCC(C)(O)C#C QXLPXWSKPNOQLE-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000010705 motor oil Substances 0.000 description 1
- 235000019508 mustard seed Nutrition 0.000 description 1
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 1
- PZYDAVFRVJXFHS-UHFFFAOYSA-N n-cyclohexyl-2-pyrrolidone Chemical compound O=C1CCCN1C1CCCCC1 PZYDAVFRVJXFHS-UHFFFAOYSA-N 0.000 description 1
- 239000000025 natural resin Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 235000021313 oleic acid Nutrition 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000006353 oxyethylene group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000005704 oxymethylene group Chemical group [H]C([H])([*:2])O[*:1] 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 235000020232 peanut Nutrition 0.000 description 1
- LTHAIAJHDPJXLG-UHFFFAOYSA-N pentan-2-ylbenzene Chemical compound CCCC(C)C1=CC=CC=C1 LTHAIAJHDPJXLG-UHFFFAOYSA-N 0.000 description 1
- TWSRVQVEYJNFKQ-UHFFFAOYSA-N pentyl propanoate Chemical compound CCCCCOC(=O)CC TWSRVQVEYJNFKQ-UHFFFAOYSA-N 0.000 description 1
- 229920006287 phenoxy resin Polymers 0.000 description 1
- 239000013034 phenoxy resin Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 239000001739 pinus spp. Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000010491 poppyseed oil Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- MCSINKKTEDDPNK-UHFFFAOYSA-N propyl propionate Chemical compound CCCOC(=O)CC MCSINKKTEDDPNK-UHFFFAOYSA-N 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000010668 rosemary oil Substances 0.000 description 1
- 229940058206 rosemary oil Drugs 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000004447 silicone coating Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 229930006978 terpinene Natural products 0.000 description 1
- 150000003507 terpinene derivatives Chemical class 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- WBYWAXJHAXSJNI-VOTSOKGWSA-M trans-cinnamate Chemical compound [O-]C(=O)\C=C\C1=CC=CC=C1 WBYWAXJHAXSJNI-VOTSOKGWSA-M 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- WEAPVABOECTMGR-UHFFFAOYSA-N triethyl 2-acetyloxypropane-1,2,3-tricarboxylate Chemical compound CCOC(=O)CC(C(=O)OCC)(OC(C)=O)CC(=O)OCC WEAPVABOECTMGR-UHFFFAOYSA-N 0.000 description 1
- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 description 1
- PHYFQTYBJUILEZ-IUPFWZBJSA-N triolein Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(OC(=O)CCCCCCC\C=C/CCCCCCCC)COC(=O)CCCCCCC\C=C/CCCCCCCC PHYFQTYBJUILEZ-IUPFWZBJSA-N 0.000 description 1
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 1
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 1
- 150000003673 urethanes Chemical class 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 229920001285 xanthan gum Polymers 0.000 description 1
- 235000010493 xanthan gum Nutrition 0.000 description 1
- 239000000230 xanthan gum Substances 0.000 description 1
- 229940082509 xanthan gum Drugs 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2093—Esters; Carbonates
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/39—Derivatives containing from 2 to 10 oxyalkylene groups
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
- A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
- A61K8/4973—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with oxygen as the only hetero atom
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/92—Oils, fats or waxes; Derivatives thereof, e.g. hydrogenation products thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/10—Washing or bathing preparations
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/12—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/14—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D317/18—Radicals substituted by singly bound oxygen or sulfur atoms
- C07D317/24—Radicals substituted by singly bound oxygen or sulfur atoms esterified
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2096—Heterocyclic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/266—Esters or carbonates
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/26—Organic compounds containing oxygen
- C11D7/267—Heterocyclic compounds
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
- C23G5/02—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents
- C23G5/032—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing oxygen-containing compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
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- Engineering & Computer Science (AREA)
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- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Birds (AREA)
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- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Dermatology (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Detergent Compositions (AREA)
- Paints Or Removers (AREA)
- Anti-Oxidant Or Stabilizer Compositions (AREA)
Abstract
描述了一种除去组合物,其具有多个磨料颗粒、有机胺、抗氧化剂、杀菌剂、着色剂、腐蚀抑制剂、共溶剂、消泡剂、染料、酶、光稳定剂、遮味剂、增塑剂、防腐剂、防锈剂、表面活性剂、增稠剂、或包含上述中的至少一种的组合;基于所述除去组合物的总重量,0至1%水;和式(1)的缩酮加合物,其中,R1是C1-6烷基,R2是氢或者C1-3烷基,各个R3、R4和R5独立地为氢或者C1-6烷基,R6和R7各自独立地为氢或者C1-6烷基,a=0-3,以及b=0-l。
Description
相关申请的交叉引用
本申请要求在2010年8月12日提交的美国临时专利申请号61/372,978和在2010年10月19日提交的美国临时专利申请号61/394,374的权益,通过参考将两个申请的内容整体并入本文中。
背景技术
本公开内容涉及羧基酯缩酮剥除和除去组合物(carboxy ester ketalstripping and removal composition),所述组合物的制造方法和所述组合物的应用。
在剥除和除去组合物(例如,油漆(涂料)剥离或涂鸦或粘合剂除去)时,通过考虑因素如溶解性、增溶活性、反应性、挥发性、毒性、环境概况(environmental profile)和成本来引导溶剂的选择。已经建立了如下理论:通过两种机理,即溶解和/或剥离(lifting)来实现从基材中除去不期望的油漆、油墨、粘合剂等。溶解是通过溶剂将不期望的材料从基材上溶解。剥离是将溶剂渗透到不期望的材料中并使其溶胀。作为溶胀的结果,材料(无论其是油漆、涂料还是其他)起皱并从基材上剥离(分离),从而使得由此可以将材料容易地从基材表面上除去。
发明内容
尽管大量用于剥除和除去组合物的溶剂是可获得的且用于商业用途,但是在本领域中对于提供溶解性、增溶活性、反应性、挥发性、毒性、环境概况和成本的有利组合的新溶剂仍然存在需求。
此外,对于可用作石油来源的溶剂的替代物的“生物来源的”溶剂存在不断增加的需求。可获得的可满足用于剥除和除去组合物的要求不断增加的技术要求的生物来源的溶剂很少。即使在可以获得这种溶剂的情况下,该溶剂也会具有各种缺点。例如,已经在脱脂用途中用作氯代溶剂的替代物的d-苧烯具有强烈的气味,可燃并且被分类为刺激物和致敏物。类似地,乙醇是容易由生物基来源获得的通用溶剂,但是其高可燃性限制了其在溶剂用途中的应用。这些溶剂的其他缺点是溶剂的化学和物理性质仅能在有限程度上进行调节。
因此,在本领域中对于提供增溶活性与反应性、挥发性、毒性、环境概况和成本的一种或多种的有利组合的用于剥除和除去组合物的替代溶剂,特别是生物来源的溶剂仍然存在需求。如果这种溶剂可以容易地被改性而对溶剂的化学和物理性质进行调节以满足特定用途的需求,则会是更加有利的。如果生物来源的溶剂提供满足一种或多种用户需求如良好的粘性、低气味、高增溶和/或剥离活性和低毒性的剥除和除去组合物,则是有利的。
除去组合物(removal composition)包含多个磨料颗粒(腐蚀微粒,abrasive particle)、有机胺、抗氧化剂、杀菌剂(抗微生物剂,杀虫剂,biocide)、着色剂、腐蚀抑制剂、共溶剂(助溶剂,cosolvent)、消泡剂、染料、酶、光稳定剂、遮味剂(odor masking agent)、增塑剂、防腐剂、防锈剂(rust inhibitor)、表面活性剂、增稠剂、或包含上述中的至少一种的组合;基于所述除去组合物的总重量,0至1%水;和式(1)的缩酮加合物:
其中,R1是C1-6烷基,
R2是氢或者C1-3烷基,
各个R3、R4和R5独立地为氢或者C1-6烷基,
R6和R7各自独立地为氢或者C1-6烷基,
a=0-3,以及
b=0-l。
制备除去组合物的方法包括将多个磨料颗粒、有机胺、抗氧化剂、杀菌剂、着色剂、腐蚀抑制剂、共溶剂、消泡剂、染料、酶、光稳定剂、遮味剂、增塑剂、防腐剂、防锈剂、增稠剂、或包含上述中的至少一种的组合与上述式(1)的缩酮加合物合并(结合,combining)。
除去基材表面上的材料的方法包括在除去条件下使基材表面上的材料与上述除去组合物接触;和将所述材料与所述基材至少部分分离。
除去基材表面上的材料的方法包括在除去条件下使基材表面上的材料与上述缩酮加合物接触;和将所述材料与所述基材至少部分分离,其中在接触期间存在0至1wt%的水。
在下面的图和详细说明中进一步描述了上述和其他实施方式。
具体实施方式
本发明人由此发现了,酮羧基酯(ketocarboxy ester),特别是乙酰丙酸酯(levulinate ester)的缩酮加合物提供可用于从表面上剥除或除去材料的性质的组合。这种剥除和除去组合物包括用于油漆剥除、涂鸦除去、油墨清洁和除去、粘合剂除去、乳香除去、光致抗蚀剂除去、蜡剥除、沥青除去、混凝土清洁、模板清洁、模具清洁、手清洁、树液/沥青除去、油渍清洁和除去、部件脱脂和发动机脱脂的制剂。缩酮加合物的不同的溶解性使得它们可用于各种组合物,特别是各种有机除去组合物。另一个优势是特定的缩酮加合物,诸如乙酰丙酸酯缩酮可以源自生物原料。
在本文中有时称作“缩酮加合物”的酮羧基酯缩酮具有通式(1):
其中,
R1是C1-6烷基,
R2是氢或者C1-3烷基,
各个R3、R4和R5独立地为氢或者C1-6烷基,
R6和R7各自独立地为氢或者C1-6烷基,
a=0-3,以及
b=0-l。
更具体地,R1是C1-6烷基,R2是甲基,各个R3、R4和R5独立地为氢或者C1-3烷基,R6是氢或者C1-6烷基,R7是氢,a=l-3,以及b=0-l。
还更具体地,R1是C1-4烷基,R2是甲基,R3是氢,R6是氢或C1-3烷基,R7是氢,a=l-2,以及b=0。
在一个具体的实施方式中,R1是C1-4烷基,R2是甲基,R3是氢,R6是氢、甲基或乙基,R7是氢,a=2,以及b=0。
还更具体地,缩酮加合物是具有式(la)的乙酰丙酸酯的1,2-丙二醇加合物:
其中R如上所限定,具体地为C1-4烷基,更具体地为乙基或丁基。当在式(la)中R1为乙基时,获得乙酰丙酸乙酯丙二醇缩酮(ethyl levulinatepropylene glycol ketal)(“EtLPK”)。
式(1)的缩酮加合物可以通过式(2)的对应酮酸酯与式(3)的多元醇的酸催化反应获得:
其中R1、R2、R3、R4、R6和R7中的每一个,以及a和b如上所限定。例如在WO09/032905中描述了反应条件。落在式(2)和(3)范围内的许多化合物可以为生物来源的。缩酮加合物由此对各种生物来源的溶剂提供进入点。例如,通过各种碳水化合物如纤维素的热化学处理制造乙酰丙酸;随后利用生物来源的烷醇酯化并利用多羟基化合物如甘油或丙二醇将乙酰丙酸酯缩酮化制得生物来源的溶剂。
在高度有利的特征中,式(1)的缩酮加合物中特定的R1、R2、R3、R4、R6和R7基团中的每一个、以及a和b的选择使得可以对缩酮加合物的化学和物理性质进行调节以实现期望的性质如增溶活性和挥发性的组合。使用单骨架(scaffold)调节这些特征的每一种的能力在设计实现上述组合物的技术要求的溶剂时提供更大的灵活性。
由此,在一个具体的实施方式中,选择特定的R1,R2,R3,R4,R6和R7基团中的每一个,以及a和b以提供期望的增溶活性,即缩酮加合物增溶溶质的能力。类似于酯和醚的官能度的存在使得缩酮加合物可以与各种溶质官能团相互作用。
缩酮加合物(1),具体地(la)因为它们的低挥发性而进一步有利,所述低挥发性对于其中除去制剂的快速挥发使得产品的重新应用成为必要的油漆和涂鸦除去会是特别期望的。挥发性在关于溶剂的大量关键性质中本身显现出来,所述性质包括沸点、蒸汽压、相对蒸发速度、可燃性、气味和挥发性有机化合物(VOC)含量。溶剂的期望的挥发性分布随用途而显著变化,且经常存在冲突的考虑因素。例如,高挥发性处理溶剂在使用后需要较少的能量以将其除去,但是在许多情况下也因为较高的可燃性而需要特殊的处理。特定的R1,R2,R3,R4,R6和R7基团中的每一个,以及a和b的适当选择可以进一步提供选择的挥发性。特别地,EtLPK具有可接受的低挥发性和低可燃性。
如上所述,缩酮加合物(1),特别是(la)可用于油漆剥除和涂鸦除去组合物。由于经常使用油漆施加涂鸦,所以涉及两种组合物。然而,还已经发现,缩酮加合物可用于除去粘合剂、乳香、油墨、光致抗蚀剂、沥青、沥青、油脂、油和其他类型的涂料。缩酮加合物具有用于这些用途的性质的优异组合,所述性质包括增溶活性、低可燃性、长工作时间、生物可降解性、非腐蚀性和低气味。
在一个实施方式中,除去组合物仅包含缩酮加合物(1),具体地(la),以及基于所述除去组合物的总重量,按重量计0至1%的水。在另一个实施方式中,除去组合物包含缩酮加合物(1),具体地(la);基于所述除去组合物的总重量,按重量计0至1%的水;以及下面更详细描述的一种或多种另外的成分,例如共溶剂和/或其他成分。
例示性共溶剂包括:
脂族烃,例如C6-30直链、支链或环状脂族烃,它们优选在环境温度下为液体且具有至少约100℃的沸点,例如,矿物油(还称作液体石蜡油(petrolatum)或液体石蜡),矿物油精(还称作挥发油或汽油),以及烃蒸馏物的低闪点馏分(例如,C-145(主要为C10-13环烷烃和异环烷烃),C-170(主要由C10-15环烷烃和异环烷烃构成),C-200(主要由C12-16环烷烃和异环烷烃构成)和215(主要由C12-15环烷烃和异环烷烃构成),得自Calumet Specialty partners);
芳族烃,例如萘,苯的C1-8烷基衍生物和萘的C1-8烷基衍生物,具体地甲苯,二甲苯(邻,间或对),异丙基苯,乙苯,均三甲苯,四甲基苯,仲戊基苯,正丁基苯,萘和甲基萘;
萜烯,例如,松节油,α-蒎烯,β-蒎烯和d-苧烯;
有机含硫化合物诸如亚砜,例如二甲基亚砜(DMSO);
氯代溶剂,例如氯代的C1-6脂族化合物如烯丙基氯,四氯化碳,氯仿,1,1-二氯乙烷,二氯***,1,2-二氯乙烯,二氯异丙基醚,氯乙烷,二氯乙烯,异丙基氯,甲基氯,全氯乙烯,二氯丙烯,1,1,2-三氯乙烷,三氯乙烯,1,2,3-三氯丙烯,和二氯甲烷(二氯甲烷或DCM);
醇,例如戊醇,正丁醇,3-丁氧基乙基-2-丙醇,苯甲醇,苄氧基乙醇,二乙氧基乙醇,二异丁基甲醇,二甲基庚醇,乙醇,2-乙基己醇,乙二醇,甘油,1-己醇,异丁醇,异丙醇,甲醇,甲基戊醇,2-甲基-1-丁醇,1-戊醇,1-丙醇,丙二醇缩酮,和2,2,4-三甲基-l,3-戊二醇单异丁酸酯(可作为UCAR FILMERTM IBT商购得自Dow Chemical Co.);
二醇醚,例如二乙二醇甲基醚,二乙二醇单-正丁基醚(可作为丁基卡必醇(Butyl CARBITOL)商购得自Dow),二乙二醇单乙基醚(可作为卡必醇(CARBITOL)商购得自Dow),二乙二醇单己基醚(可作为己基卡必醇(Hexyl CARBITOL)商购得自Dow),二乙二醇单甲基醚(可作为甲基卡必醇(Methyl CARBITOL)商购得自Dow),二乙二醇单丙基醚(可作为丙基卡必醇(Propyl CARBITOL)商购得自Dow),二乙二醇正丁基醚乙酸酯(可作为丁基卡必醇TM乙酸酯(Butyl CARBITOLTM Acetate)商购得自Dow),二丙二醇单丁基醚(可作为DOWANOLTM DPnB商购得自Dow),二丙二醇单甲基醚(可作为DOWANOL DPM商购得自Dow),二丙二醇单丙基醚(可作为DOWANOL DPnP商购得自Dow),二丙二醇叔丁基醚,乙二醇甲基醚乙酸酯(可作为甲基乙酸酯(甲基溶纤剂乙酸酯(乙酸甲氧乙酯,Methyl CELLOSOLVE Acetate))商购得自Dow),乙二醇单丁基醚(可作为丁基溶纤剂(Butyl CELLOSOLVE)商购得自Dow),乙二醇单己基醚(可作为己基溶纤剂(Hexyl CELLOSOLVE)商购得自Dow),乙二醇单丙基醚(可作为丙基溶纤剂(Propyl CELLOSOLVE)商购得自Dow),乙二醇正丁基醚乙酸酯(可作为丁基溶纤剂乙酸酯(Butyl CELLOSOLVEAcetate)商购得自Dow),乙二醇苯基醚(可作为“DOWANOLTM EPh”商购得自Dow),七乙二醇单苄基醚,七乙二醇单苯基醚,六乙二醇单苄基醚,六乙二醇单苯基醚,五乙二醇单苄基醚,五乙二醇单苯基醚,丙二醇乙基醚,丙二醇甲基醚乙酸酯(可作为DOWANOLTM PMA商购得自Dow),丙二醇单丁基醚(可作为DOWANOL PnB商购得自Dow),丙二醇单甲基醚(可作为DOWANOL PM商购得自Dow),丙二醇单丙基醚(可作为DOWANOL PnP商购得自Dow),丙二醇苯基醚(可作为“DOWANOL PPh”商购得自Dow),四乙二醇单苄基醚,四乙二醇单苯基醚,三乙二醇甲基醚,三乙二醇单苄基醚,三乙二醇单苯基醚,三丙二醇甲基醚(可作为DOWANOL TPM商购得自Dow),和三丙二醇正丁基醚(可作为DOWANOL TPnB商购得自Dow);
丙二醇单苯基醚的水溶性乙氧基化物(优选地,每个分子包含平均至少2个氧乙烯部分);
水溶性或水分散性聚合胺诸如聚(乙烯亚胺);
酰胺诸如乙酰胺基苯酚,N,N-二甲基甲酰胺(DMF)和乙酰替苯胺,以及环酰胺诸如l-甲基-2-吡咯烷酮(NMP),N-乙基-2-吡咯烷酮,N-异丙基-2-吡咯烷酮,N-环己基-2-吡咯烷酮,2-羟基乙基-2-吡咯烷酮,N-二甲基氨基丙基-2-吡咯烷酮,乙烯基-吡咯烷酮和2-吡咯烷酮;
胺诸如2-(2-氨基乙氧基)乙醇,2-乙酰基-1-甲基吡咯,2-氨基-2-甲基-1-丙醇烷醇胺(例如,正丁基二乙醇胺,二乙醇胺,二异丙醇胺,二甲基乙醇胺,乙醇胺,异丙醇胺,甲基异丙醇胺,苯基二乙醇胺和三乙醇胺),环胺(例如,N-甲基吡咯烷,N-甲基吡咯,吗啉和噁唑烷),正丁基氨基乙醇,二乙基氨基乙醇,二甘醇胺,2-甲基氨基乙醇和三烷基胺(例如三乙基胺);
酮和环酮诸如异丁基庚基酮,异佛尔酮,甲基乙基酮,甲基异丁基酮,二异丁基酮,双丙酮醇,苯乙酮,甲基正戊基酮,环己酮和环庚酮;
碳酸二烷基酯诸如碳酸二甲酯,碳酸二乙酯,碳酸二丙酯,碳酸二异丙酯和碳酸二丁酯;
环碳酸酯诸如碳酸亚丙酯和碳酸亚乙酯;
单酯诸如乙酸戊酯,乙酸苄基酯,苯甲酸苄基酯,乙酸丁酯,乙酸乙酯,丙酸乙酯,乳酸乙酯,乙酸异丁酯,乙酸异丙酯,丙酸正丁酯,丙酸正戊酯,乙酸正丙酯,丙酸正丙酯,乳酸丁酯,C6-22饱和或不饱和羧酸的C1-4烷基酯诸如C6-14不饱和脂肪酸的甲基酯;脂肪酸的甘油酯,包括源自植物油诸如亚麻籽,椰子,棕榈,大豆,棉籽,落花生,葵花,油菜,芝麻,橄榄,玉米,红花,棕仁,蓖麻油,花生,鱼,猪油,芥菜籽,罂粟籽,松节油和妥儿油的脂肪酸的甘油酯,以及3-乙氧基丙酸乙酯(可作为UCARTM Ester EEP商购得自Dow Chemical Co.);
二元酸酯诸如己二酸二甲酯,琥珀酸二甲酯,戊二酸二甲酯,丙二酸二甲酯,己二酸二乙酯,琥珀酸二乙酯,戊二酸二乙酯,琥珀酸二丁酯,戊二酸二丁酯,以及以交易名称DBETM,DBE-3,DBE-4,DBE-5,DBE-6,DBE-9,DBE-IB和DBE-ME得自Invista的产品;
美国专利号7179775中所述的烷氧基化的芳族醇,特别是每个分子包含至少一个芳族环和通式-(CR1R3-CR2R4-O)n-R5的烷氧基化单元的烷氧基化的芳族醇,其中:R1,R2,R3和R4各自独立地为氢或者甲基;R5是氢,C1-6烷基或苯基;以及n是2-10,其中烷氧基化单元直接或者通过醚(氧)键或氧亚甲基(-CHR8O-)键连接至芳环,其中R8是氢或C1-4烷基。可以使用包含上述共溶剂的任一种或多种的组合。在一个实施方式中,共溶剂是NMP。
缩酮加合物与共溶剂的比率可以根据缩酮加合物、共溶剂和预期目的而广泛变化,且可以全部按体积计为1:99至99:1,具体地10:90至90:10,更具体地20:80至80:20,30:70至70:30或40:60至60:40。
除去组合物可以配制为例如,除漆剂(油漆除去剂,paint remover)、涂鸦除去剂(graffiti remover)、油墨除去剂、粘合剂除去剂、乳香除去剂(mastic remover)、光致抗蚀剂除去剂、蜡除去剂、沥青除去剂、混凝土清洁剂(concrete cleaner)、模板清洁剂(form cleaner)、手清洁剂、身体清洁剂、树液除去剂(sap remover)、油除去剂或油脂除去剂(润滑脂除去剂,grease remover)。单一组合物可具有多于一种应用,例如,可以将单一组合物用作油漆和油墨除去剂,用作油漆、油和油脂除去剂。
由此,除去组合物可包含其他成分以辅助组合物的功能,所述其他成分例如磨料颗粒、有机胺促进剂、有机酸促进剂、抗氧化剂、防锈添加剂、杀菌剂、着色剂、腐蚀抑制剂、共溶剂、消泡剂、染料、酶、光稳定剂、遮味剂(包括香水)、增塑剂、防腐剂、表面活性剂(包括两性、阴离子、阳离子、非离子或两性离子)、增稠剂以及包含上述中的至少一种的组合。应理解,单一添加剂可具有多于一种功能且具有所述功能(例如,作为共溶剂)的添加剂的特征不将添加剂排除在执行另一种功能之外。除去组合物的各添加剂的浓度可以随除去组合物的成分、待除去的材料的类型和进行材料除去的速度而变化。本领域的技术人员使用标准实验方法和下面提供的准则可以容易地确定用于特定用途的最佳浓度。
在一个具体实施方式中,除去组合物包含酰胺共溶剂,例如NMP,胺促进剂,例如吗啉,增稠剂,例如纤维素增稠剂诸如甲基纤维素和表面活性剂。
在另一个具体实施方式中,除去组合物包含亚砜共溶剂,例如二甲基亚砜,胺促进剂,例如吗啉,增稠剂,例如纤维素增稠剂诸如甲基纤维素和表面活性剂。
有机胺促进剂可包括作为共溶剂在上面列出的那些。认为促进剂通过化学攻击涂料的有机粘合剂并由此减弱涂料的粘合力和内聚力而强化了组合物的性能。例示性胺促进剂包括乙醇胺、二乙醇胺、乙二胺四乙酸、吗啉、三乙醇胺、三乙基胺和2-(N,N'-二乙基氨基)乙醇)。当用作添加剂时,胺促进剂可以以0.1至20wt.%或1至10wt.%的量存在,但是这些量仅是例示性的。
例示性有机酸促进剂包括C1-22羧酸(例如,甲酸,乙酸,丙酸,油酸,草酸和羟基乙酸)。当用作添加剂时,有机酸促进剂可以以0.1至20wt.%或1至10wt.%的量存在,但是这些量仅是例示性的。
特别地在金属容器中提供组合物的情况下或者当存在酸促进剂时,可以存在腐蚀抑制剂。腐蚀抑制剂可以为例如具有油溶性部分和水溶性部分两者的分子,诸如以按重量计约0.05%至约2%,具体地约0.25%至约1.0%的量包含胺官能度的两性表面活性剂,诸如可作为两性表面活性剂得自Cognis Corporation的N-月桂基亚氨基二丙酸酯二钠。其他腐蚀抑制剂包括脂肪酸的胺皂和脂肪烷醇酰胺诸如C8至C18脂肪烷醇酰胺,其实例包括可得自Cognis Corporation的烷醇酰胺。这种腐蚀抑制剂也可以用于会因为在清洁组合物中存在水而生锈或腐蚀的表面上,诸如金属表面如铁和钢等的后涂布抗腐蚀效果。
除去组合物还可以包含有效量的遮味剂,诸如精油、合成香料、香水等,例如,龙涎香、龙脑及其酯、香芹酮、海狸香、麝猫香、肉桂醛、柠檬醛、丁香油、白松香、茉莉黄、苧烯、里哪醇及其酯、蒎烯(α、β等)、迷迭香油、檀香、萜品醇、萜品烯等;苯甲醛、苯偶姻、异戊酯(香蕉);丙酸异丁酯(朗姆酒);氨基苯甲酸甲酯(葡萄);乙酸苄基酯(桃)、二聚戊烯、丁酸甲酯(苹果);丁酸乙酯(菠萝);乙酸辛酯(桔子);乙酸正丙酯(梨);乙酸乙基苯酯(蜂蜜)等。这种遮味剂的有效量可以被本领域的技术人员容易地确定,且按重量计可以例如为除去组合物的约0.25%至约2.50%,具体地约0.4%至约1.0%。
例示性增塑剂包括邻苯二甲酸酯,例如邻苯二甲酸二丁酯,邻苯二甲酸二乙基己基酯和邻苯二甲酸二乙酯;脂族二酯,例如己二酸二辛酯;对苯二甲酸酯,例如对苯二甲酸二辛酯;柠檬酸酯,例如乙酰基柠檬酸三乙酯和乙酰基柠檬酸三正丁酯;缩酮基增塑剂,诸如在PCT申请WO2010/151558中所述的那些,或者包含上述中的至少一种的组合。当使用时,基于所述除去组合物的总重量,增塑剂以约0.1至约10wt.%的量存在。
可以根据用途利用各种表面活性剂,且表面活性剂可以为两性、阴离子、阳离子、非离子或两性离子的。可以存在表面活性剂或者表面活性剂的组合以便提高待除去的涂料的润湿性并加快活性成分的渗透。另外,表面活性剂可以在除去涂料之后促进基材的水漂洗和水清洁。例示性两性表面活性剂包括具有式RR'R"N→O的胺氧化物化合物,其中各个R、R'和R"独立地为可任选地包含一个或多个P、O、S或N杂原子的C1-C24烷基,芳基或者芳基烷基基团。例示性两性表面活性剂还包括式RR'R"N+(CH2)nC(O)O-的甜菜碱化合物(内铵盐化合物),其中各个R、R'和R"独立地为可任选地包含一个或多个P、O、S或N杂原子的C1-C24烷基、芳基或者芳基烷基基团,并且n是约1至约10。可以使用包含上述中的至少一种的组合。
例示性阴离子表面活性剂包括烷基苯磺酸酯的水溶性盐诸如C10-14烷基苯磺酸的异丙基胺盐,和/或C8-14脂肪醇硫酸酯,烷基硫酸酯类,烷基聚乙氧基醚硫酸酯,链烷烃磺酸酯,α-烯烃磺酸酯和磺基琥珀酸酯,α-磺基羧酸酯和它们的酯,烷基甘油基醚磺酸酯,脂肪酸单甘油硫酸酯和磺酸酯,烷基苯酚聚乙氧基醚硫酸酯,在脂肪酸基团中包含约6至约20个碳原子且在酯基团中包含约1至约10个碳原子的α-磺化的脂肪酸的水溶性盐或酯等。当存在时,基于组合物的重量,阴离子表面活性剂可以以按重量计约0.1至约15%,按重量计约3至约12%,且最优选按重量计约5至约10%的量存在于组合物中。可以使用包含上述中的至少一种的组合。
除了阴离子表面活性剂之外或者代替阴离子表面活性剂,可以存在短链表面活性剂,例如C3-C6醇,二醇,二醇醚诸如丙二醇正丁基醚,吡咯烷酮,二醇醚酯等。可以使用包含上述中的至少一种的组合。
例示性阳离子表面活性剂包括具有式RR'R"R"'N+X的季胺化合物,其中各个R、R'、R"和R'"独立地为可任选地包含一个或多个P、O、S或N杂原子的C1-C24烷基、芳基或者芳基烷基基团,且X是F、C1、Br、I或者烷基硫酸盐(或酯)。可以使用包含上述中的至少一种的组合。
例示性非离子表面活性剂包括具有1至约20个环氧乙烷基团(例如,约9至约20个环氧乙烷基团)的醇乙氧基化物(例如,C6-C24或C6-C16醇乙氧基化物),具有1至约100个环氧乙烷基团(例如,约12至约20个环氧乙烷基团)的烷基苯酚乙氧基化物(例如,C6-C24或者C8-C10烷基苯酚乙氧基化物),具有1至约20个糖苷基团(例如,约9至约20个糖苷基团)的烷基多糖苷(例如,C6-C24或C6-C20烷基多糖苷)。可以使用包含上述中的至少一种的组合。
作为一般指导,表面活性剂的量可以为除去组合物的总重量的约0.1至约20%,约0.1至约15%或者约2至约15%。
可以存在增稠剂以调节除去组合物的流变性质。例如,通常通过将涂料除去剂喷射到喷漆室上而进行将部分干燥的油漆从自动喷漆室中除去。涂料除去剂必须足够薄以易于喷雾,但是必须在低剪切条件下快速地建立粘度以有效地粘在垂直表面上。如果要涂覆涂料除去剂,则较高粘度的制剂是通常期望的,而在将被涂布的基材浸泡在槽中的情况下,通常使用不含添加的增稠剂的低粘度制剂。增稠剂还可以用于通过在涂布到被涂布的基材上之后,降低挥发性成分的蒸发速度而提高涂料除去剂的有效性。在组合物中使用增稠剂使得能够将组合物涂布到垂直表面上而不伴随任何由其的滴落或流出,并且还抑制组合物到多孔基材如砖或混凝土中的散逸。
例示性增稠剂是天然或合成粘土,包括膨润土,锂蒙脱石,蒙脱石和其他硅酸盐诸如可用等级的BENTOLITETM,C1AYTONETM和GELWHITETM膨润土,PERMONTM蒙脱石,CLOISITETM镁铝硅酸盐,LAPONITETM硅酸盐和GARAMITETM硅酸盐(所有都可得自SouthernC1ay Product,Inc.),以及可用等级的OPTIGELTM膨润土,锂蒙脱石,蒙脱石和其他粘土(所有都得自Sued-Chemie Group);有机粘土化合物诸如四烷基铵膨润土的硬脂酸酯;树胶和其他多糖诸如角叉菜胶(例如,GENUVISCOTM X-906-02(来自CP Kelco)),肉桂胶,迪特胶(例如,GEOVISTM XT,KELCO-CRETETM80,KELCO-CRETE200和KOC617(所有都来自CP Kelco)),结冷胶(例如,KELCOGELTM,KELCOGEL F和KELCOGEL LT100(所有都来自CP Kelco)),瓜尔豆胶,***胶,黄蓍胶,刺槐豆胶,威兰胶和黄原胶(例如,KELZANTM,KELZAN AR,KELZANASX,KELZAN ASX T,KELZAN CC,KELZAN HP,KELZAN RD,KELZAN S,KELZAN ST,KELZAN T,KELTROLTM,KELTROL T和KELTROL TF(所有都来自CP Kelco),以及VANZANTM和VANZAN D(两者都来自R.T.Vanderbilt Co.));水解胶体诸如NOVEGUMTM C865,NOVEGUM C866和NOVEGUM G888(所有都来自Noveon,Inc.);藻朊酸盐诸如琼脂;纤维素醚诸如乙基纤维素,羟基乙基纤维素,乙基羟基乙基纤维素,甲基纤维素,羟基丙基纤维素,羟基丙基甲基纤维素和其他烷基或者羟基烷基纤维素醚,例如,可作为如下商购获得:METHOCELTMK15MDGSE,METHOCEL K4MDGSE,METHOCEL311,METHOCELF4M PRG和METHOCEL O(所有都来自Dow),XDS8898.5纤维素醚(来自Dow),以及KLUCELTM H,KLUCEL M或者KLUCEL G(所有都来自Ashland,Inc.);丙烯酸类均聚物或共聚物,例如可以用包含缔合或非缔合增稠剂的盐中和的那些物质,诸如ACUSOLTM801s,ACUSOL810,ACUSOL810A,ACUSOL820,ACUSOL823和ACUSOL830丙烯酸酯聚合物(所有都来自Rohm&Haas Co.)或者可以被交联(例如,用聚烯基聚醚)的那些物质,包括CARBOPOLTM674,CARBOPOL676,CARBOPOLETD2691,CARBOPOL ETD2623,CARBOPOL EZ-3,CARBOPOLEZ-3A,CARBOPOL EZ-4和CARBOPOL ULTREZTM21(所有都来自Noveon,Inc.);PEMULENTM1622共聚物(来自Noveon,Inc.);聚环氧乙烷(例如,高分子量聚环氧乙烷)诸如聚乙二醇和甲氧基聚乙二醇;聚乙烯醇;聚乙烯基吡咯烷酮;淀粉;聚氨酯,包括RHEOLATETM266(来自Elementis Specialties,Inc.),以及可用等级的OPTIFLOTM缔合增稠剂(所有都可得自Sud-Chemie Group);以及甲基乙烯基醚/马来酸酐共聚物。其他可能的增稠剂包括疏水改性的乙氧基聚氨酯(HEUR)增稠剂,疏水改性的碱溶性乳液(HASE)增稠剂,疏水改性的羟基乙基纤维素(HM-HEC)增稠剂和HEUR-ASE组合增稠剂。可以使用包含上述中的至少一种的组合。
基于除去组合物的总重量,增稠剂可以以约0.1至约30wt.%,具体地约2至约20wt.%,更具体地约3至约10wt.%的量使用。
制备除去组合物的方法包括将缩酮加合物(1),具体地(la)与任何共溶剂或者其他成分合并(结合)以形成除去组合物。缩酮加合物和添加剂可以以任何适合的顺序添加至组合物中存在的一种或多种其他成分中,例如增稠剂和酰胺共溶剂中以在除去组合物提供这些添加剂。
当与共溶剂或者其他成分一起使用时,可以以浓缩物的形式提供除去组合物。通常将浓缩物在水中稀释以用作起作用的水基除去组合物。在一个实施方式中,可以提供两部分浓缩包(两组分浓缩包,two-part concentratepackage),其通常包含部分(组分)A和部分B,其中各部分包含可能与其他部分反应的组分,例如在部分A中包含缩酮和胺且在部分B中包含有机碱。
或者,除去组合物可以以可用于除去或者清洁组合物的其他形式,例如凝胶、擦拭布(wipe)、气溶胶等配制。除去组合物可以通过添加有效量的胶凝剂如熔融二氧化硅、有机胶、聚合物、共聚物、石蜡、膨润土与纤维素醚如可作为纤维素醚商购得自Dow Chemical的甲基纤维素和羟丙基甲基纤维素,以凝胶形式配制。擦拭布通常为用凝胶或液体除去组合物浸渍的天然或合成布片。当作为气溶胶使用时,如本领域中已知的,除去制剂利用推进剂在加压下配制。
从基底中除去材料的方法包括:在进行除去的条件下使材料与包含缩酮加合物(1),具体地(la)的组合物接触例如有效地溶解和/或剥离(lift)所述材料的时间;以及将溶解和/或剥离的材料与所述基底分离。如本文中所用的,“溶解”包括通常称作软化的材料的部分溶解,使得可以通过漂洗或机械作用将材料从基底上进一步除去。当然,也可以通过将材料分离而将除去组合物至少部分除去。
除去组合物可用于除去各种材料,通常为可以被有机溶剂溶解或软化的材料。实例包括材料诸如用于各种基底和用于室内或室外应用的油墨,所述基底包括纸、木头、塑料、金属、织物、陶瓷、石头、皮肤;粘合剂和密封剂,例如硅酮、聚氨酯、环氧树脂、聚乙酸乙烯酯(包括与乙烯的共聚物)、酚醛树脂、氨基树脂、氰基丙烯酸酯、聚酯、聚酰胺、橡胶(苯乙烯-丁二烯橡胶和天然橡胶)或者丙烯酸类粘合剂和密封剂;乳香;光致抗蚀剂;蜡,例如地板蜡或蜂蜡;沥青;树液(如本文中所用的,包括沥青、松香、焦油和天然树脂如树液);残留在模板或模具中的材料,例如聚合物诸如醇酸树脂、聚缩醛、聚丙烯酸酯、聚丙烯酸、聚酰胺、聚碳酸酯、聚酯、聚醚、聚乙烯、聚酰亚胺、聚苯乙烯、聚氨酯、聚乙烯基(polyvinyls)、硅酮类、天然和合成橡胶等、以及聚合物添加剂;油脂,例如硅酮和石油基油脂;油,包括机油;以及油漆、面漆和其他涂料,例如,醇酸磁漆、丙烯酸磁漆、聚酯、聚氨酯、环氧树脂涂料、乳胶漆、油基油漆、虫漆、酚醛树脂涂料、树胶清漆、硅酮涂料、聚乙烯基、聚肉桂酸乙烯酯、聚酰胺、聚酰亚胺、聚丙烯酸烷基酯、聚甲基丙烯酸烷基酯、干性油、聚丙烯酸乙烯基酯和纤维素树脂。
可以从合理地抵抗除去组合物的表面上除去材料,所述表面包括特别是如果利用蜡或其他保护材料处理的天然和合成布、木头、硬纸板和涂料纸,玻璃,热固性树脂,热塑性树脂,陶瓷,石头,砖石基底,水泥或金属(例如,铝合金,锌合金,不锈钢或镀锌钢)。可以将除去组合物进一步用于人体的一部分,例如手或头发以及动物。
尽管可以许多方式,例如以气溶胶形式或者诸如通过标准喷嘴的其他喷雾手段;刷涂;滴涂;涂布;诸如由挤压瓶或刷子以凝胶形式涂布等完成使表面与除去组合物接触的方法,但是可以具体提及点浸(bit immersion)和喷雾。如果被清洁的表面容易进入,则可以使用喷雾。喷雾压力通常为1.3巴至8.0巴绝对压力。碰撞除去组合物的机械力促进材料的除去。另一方面,如果被清洁的表面具有凹陷或不易进入的其他形状,则可以使用浸渍。当然,两种方法可以组合使用和/或以对本领域技术人员显而易见的方式变化。在接触期间或之后,可以使用机械作用如刮擦、剥落、摩擦、擦拭等以提高接触和/或帮助溶解和/或剥离。
将材料从表面上有效程度地溶解和/或剥离所需要的时间取决于材料的性质和厚度,包括成分浓度的除去组合物的组成,组合物的温度和其他因素。利用一些材料和在一些条件下,几分钟(例如,2-3分钟)的接触时间可以是足够的。当使用除去组合物时的操作温度可以为0至180℃以上,具体地15至90℃或21至55℃。在环境温度下进行处理是最方便的,但是通过根据需要对涂料除去剂和/或基底进行加热,可以缩短剥离时间。可以通过诸如利用加热枪局部施加热或者诸如利用电加热器、红外加热器等更普遍地施加热,实现加热。然而,应理解,本领域技术人员可以通过最少的实验确定用于特定除去用途的最佳条件。较高的温度通常提高将材料从表面上除去的速度。
将缩酮加合物和溶解的材料与基底分离可以包括机械作用诸如刮擦、剥落、摩擦、擦拭等,或者利用附加的除去组合物或其他溶剂漂洗基底,所述溶剂包括水或者水与有机溶剂的水性混合物。
本文中所述的除去组合物可以因此被配制以用于各种应用,诸如油漆除去(包括清洁和剥除)、涂鸦除去、油墨除去、粘合剂除去、乳香除去、光致抗蚀剂除去、蜡除去(包括蜡剥除)、沥青除去、混凝土清洁、模板清洁、模具清洁、手清洁、树液除去、油除去(包括清洁油渍)、脱脂(包括部件脱脂和发动机脱脂)。
下列非限制性实施例进一步说明了本发明的各种实施方式。
实施例
实施例1
在本实施例中将乙酰丙酸乙酯甘油缩酮(ethyl levulinate glycerolketal)(“EtLGK”,其中在式(1)中,R1和R2为甲基,a=2,b=0,R6是氢且R7是羟基亚甲基)和EtLPK表征并与各种已知溶剂进行比较,特别是乙二醇丁基醚(EGBE),二丙二醇甲基醚(DPM),丙二醇甲基醚乙酸酯(PMA),二元酸酯(DBE),d-苧烯(DL)和豆油酸甲酯(soy methyl ester)(SME)。
利用各种聚合物的溶解性研究显示了缩酮加合物(1),具体地(la)的溶剂化有效性。在这些实验中,在室温下将0.5g树脂和4.5g溶剂搅拌24小时之后进行溶解性观察。基于目视观察,溶解性评价为1(完全溶解)至6(无效果)的范围。
表1
溶解性基于溶剂-聚合物混合物的目视观察,使用下列评价方案:l=完全可溶,2=大部分可溶,3=强烈溶胀/轻微可溶,4=溶胀,5=很少溶胀,6=无可见效果。
被试验的树脂为热塑性丙烯酸类树脂Paraloid B-72和B-82(Rohm and HaasCompany),柔性聚氨酯Desmocoll176和406(Bayer MaterialScience LLC),乙酸丙酸纤维素CAP-482-0.5(Eastman Chemical Company),固体环氧树脂D.E.R.661(The DowChemical Company)和EPON1001F(Momentive Specialty Chemicals Inc.),苯氧基树脂PKHH(InChem Corporation),聚乙烯醇缩丁醛Butvar B-76(Solutia,Inc.)和聚乙酸乙烯酯(Sigma-Aldrich Corporation)。
表1中的数据显示,EtLPK溶解各种普通聚合物,出乎意料地优于EtLGK且具有与石油基溶剂乙二醇丁基醚(EGBE)、二丙二醇甲基醚(DPM)、丙二醇甲基醚乙酸酯(PMA)和二元酸酯(DBE)类似的性能。在其溶解普通聚合物的能力方面,EtLGK和EtLPK两者都显著地优于生物来源的溶剂豆油酸甲酯(SME)和d-苧烯(DL)。
海度班溶解参数(Hildebrand solubility parameter)由EtLGK和EtLPK各自的蒸发热和摩尔体积确定。将EtLGK和EtLPK的海度班数确定并示出在表2中。EtLGK的值较高反映了羟基基团的存在。
表2
表3示出了EtLGK、EtLPK、乙醇、丙二醇甲基醚(PM)和乙二醇丁基醚(EGBE)的可燃性。表3还示出了这些化合物在由加州空气资源委员会(CARB)建立的低蒸汽压(LVP)标准下的状况,所述标准限制了消费者和公共设施用清洁产品以及特定的个人护理产品和自动护理(aftercare)产品中的总VOC含量。
表3
*加州环境保护局空气资源委员会,CARB LVP免检标准(2010)。
表3中的数据显示,EtLGK和EtLPK是不可燃的并且具有满足免检用于消费品的CARB规定的低蒸汽压的标准的足够高的沸点。乙醇和普通的二醇醚不能满足CARB LVP免检标准。
如表4中所示,相对于2,2,4-三甲基-l,3-戊二醇单异丁酸酯(“TEXANOL”,以商标TEXANOL得自Eastman)试验EtLPK、EtLGK和EtLGK-乙酸酯(其中在式(1)中,R1和R2为甲基,a=2,b=0,R6是氢和R7是-CH2OC(O)CH3))的挥发性。在打开的TGA盘中在110℃下确定挥发性。
表4
表4中的数据显示,EtLGK乙酸酯的挥发性仅略高于EtLGK(对TEXANOL的相对挥发性=0.20),而EtLPK的挥发性高于Texanol(对TEXANOL的相对挥发性=1.5)。
实施例2
作为涂鸦除去制剂中的DBE的替代物,对EtLGK和EtLPK进行试验。通过Massachusetts-Lowell大学的TURI实验室对净溶剂比较它们除去涂鸦的能力。在每个试验中,使用手提式拭子利用Dayetek Daye Black快干式平版印刷油墨涂布一组不锈钢和木头试样;利用Barnes Group BowmanDistribution Industrial Finish Gloss Black喷漆24700号涂布第二组不锈钢和木头试样。使经涂布的试样静置几小时以将涂布的油墨/油漆干燥。
在第一试验中,将三种试样放入加德纳直线式耐洗刷性装置(GardnerStraight Line Washability unit)中。将Kimberly-C1ark Wypal增强纸巾连接到清洁拖运器(sled)上并利用5-7次除去溶液的喷雾浸透。利用相同的清洁除去溶液(EtLGK、EtLPK、EtLGK和EtLPK的50:50共混物以及DBE)将各试样喷雾7-10次。将清洁装置运行20个循环(~33秒)。在清洁最后,进行目视管擦,并对每种清洁溶剂将试样从最好到最差进行评定。将结果示于表5中。
表5
喷漆是两种污染物中较容易被除去的且使用30秒手动清洁除去。对于从不锈钢上除去油墨,两种缩酮溶剂都被评定为高。对于用于油墨除去的两种表面,EtLPK被评定为四种溶剂中最有效的。根据目视试验,EtLPK在除去油墨时特别有效。
在第二试验中,使用与第一实验中相同的程序,不同之处在于,对试样进行重量判定-在清洁前对试样进行称重以获得初始重量,然后在清洁后再次进行称重。表6显示了使用EtLGK、EtLPK、EtLGK和EtLPK的50:50共混物以及DBE,对于每种试样,土壤的添加量,残余量和效率。重量分析对于来自木头试样的两种土壤因为最终“净”重量的重量增加而是不确定的;因此,仅将不锈钢结果示出在表6中。
表6
对于油墨,DBE对于除去百分数给出最高值,而EtLPK对于油漆除去给出最高值,但是在两种情况下,标准偏差都足够大而使得难以得出可靠的结论。
通过与上述相同的程序进行第三试验,不同之处在于,运行清洁装置,直至将试样完全清洁或者不从表面上除去另外的污染物时(通过在至少40个循环之后观察纸巾状况而确定);记录循环总数。将各溶剂的循环数示出在表7中。
表7
在这种情况下,对于从不锈钢上清洁油墨和油漆两者,EtLPK需要最少的总循环数。DBE在木头上进行最好,但是没有一个产品将全部油漆从木头表面上除去-油墨和油漆两者在木头的纹理中残留可见的痕迹。总之,EtLPK和DBE达到终点所需要的循环数类似。
实施例3
将EtLPK配制为表8中所示的NMP基脱漆剂A。
表8
将表8的脱漆剂制剂A与商品B,Zinsser Magic Strip Citrus-Action Gel进行比较,后者包含NMP、二元酸酯和乙醇胺(具体量未知)。使用ASTMD6189中所述的规定在丙烯酸类涂料、醇酸树脂涂料和聚氨酯涂料上试验脱漆剂制剂。将试验结果示出在表9中。
表9
表9中的数据显示,在几乎全部情况下,根据本发明的脱漆剂制剂A都优于比较商品B。
实施例4
如表10中所示,将EtLPK配制为脱漆剂制剂中的DBE和豆油酸甲酯的均等替代物以除去不同成分和水平的混淆效果。将Methocell311代替Mecellose9860用作增稠剂。将结果示出在表11中。
表10
表11
在通常配制的脱漆剂体系中,EtLPK显示比豆油酸甲酯更好的性能。EtLPK与DBE的比较在一种情况下显示优越的结果,在一种情况下显示同等的结果且在两种情况下显示较差的结果。
实施例5
利用1密耳(0.025mm)刮涂棒将黑色紫外线可固化的印刷油墨(Kolorcure Series7500超致密黑色UV可固化印刷油墨)涂布到压光并磨光的铝钢Q-板(利用丙酮和纸巾清洁过的)上并利用400W金属卤化物灯泡在Loctite Zeta7401UV室中固化10分钟。以2英寸(51mm)的条通过刷子将比较溶剂制剂(Soy-Sol2300)和EtLPK涂布到铝板上。在2.5小时之后,EtLPK易于利用2英寸(51mm)塑料油灰刀除去涂料,而Soy-Sol仅除去接触面积上的涂料的10%。在钢涂布板上重复相同的试验。在5小时之后,EtLPK除去接触面积中的涂料的50%,而Soy-Sol除去接触面积中的涂料的0%。
实施例6
将1.33g未固化的黑色印刷油墨样品(Lancer Group Excalibur DirectPrint500Black,热固化制剂)放入三个单独的20-mL闪烁管中。向每个管中分别添加10g EtLPK、DBE或Soy-Sol2300溶剂组合物。将管盖好并机械振荡,直至溶解。所有溶液都变成乌黑色。EtLPK在60分钟内完全溶解样品,而在60分钟混合时间时在包含Soy-Sol2300的管中残留10%的样品,且在包含DBE的管中残留50%的样品。
实施例7
对EtLPK、d-苧烯和Steposol SB-W(豆油酸甲酯)比较它们除去紫外线(UV)固化油墨的能力。以1密耳(1.02mm)湿膜使用刮涂棒在标准乙烯基地砖上涂布Kolorcure7500(75-112)超致密黑色UV可固化印刷油墨。在Loctite Zeta7401中使用UV光将膜固化3分钟。将溶剂浸透到固定至16盎司圆头锤的圆边的粗棉中。将锤子连接至以3英寸(7.62cm)冲程将锤子来回移动的电动机。计算双摩擦冲程的总数,直至白砖(white tile)通过除去的黑色油墨显示出来。将结果示出在表12中。
表12
运行 | 溶剂 | 双摩擦 |
1 | 去离子水 | 500+ |
2 | EtLPK | 92 |
3 | d-苧烯 | 133 |
4 | 豆油酸甲酯 | 148 |
结果显示,与其他溶剂和对照物水相比,EtLPK在除去UV油墨时具有优势。
实施例8
通过利用乳胶手套将粘合剂手动擦拭到4-英寸×1-英寸(10.16cm×2.54cm)钢板上,并在室温下固化24小时将填缝胶(Loctite Polyseamseal AllPurpose Adhesive Caulk(Henkel))涂布到板上。然后,使用在280rpm下旋转的搅拌棒在恒定搅拌下将经涂布的板浸渍到90wt%EtLPK和10wt%Tomadol25-9表面活性剂溶液的溶液中。将经涂布的板在搅拌的溶液中浸泡1、2、4和8小时。在每个间隔处,从每个溶液中拉出1个板并利用布擦拭以观看除去了多少粘合剂,如下表中所记录的。还使用45%d-苧烯/45%Steposol SB-W/10%Tomadol25-9的混合物进行了比较例。将结果示出在表13中。
表13
运行 | 溶剂 | 洗涤循环(小时) | 观察结果 |
1A | EtLPK | 1 | 软化,20%除去 |
1B | EtLPK | 2 | 软化,35%除去 |
1C | EtLPK | 4 | 脱层,100%除去 |
1D | EtLPK | 8 | 严重脱层,100%除去 |
2A | d-苧烯/豆油酸甲酯 | 1 | 未软化或除去 |
2B | d-苧烯/豆油酸甲酯 | 2 | 未软化或除去 |
2C | d-苧烯/豆油酸甲酯 | 4 | 未软化或除去 |
2D | d-苧烯/豆油酸甲酯 | 8 | 未软化或除去 |
结果显示,在粘合剂填缝胶的所有时间间隔处,EtLPK都进行得比d-苧烯/豆油酸甲酯/Tomadol溶液好。在利用d-苧烯/豆油酸甲酯浸泡8小时之后的最终膜显示无软化或脱层的标记。
实施例9
通过利用乳胶手套将粘合剂手动擦拭到4-英寸×1-英寸(10.16cm×2.54cm)钢板上,并在室温下固化24小时将粘合剂(Liquid Nails,SmallProject Repair Adhesive(Akzo Nobel))涂布到板上。然后,使用在280rpm下旋转的搅拌棒在恒定搅拌下将经涂布的板浸渍到90wt%EtLPK和10wt%Tomadol25-9表面活性剂溶液的溶液中。将经涂布的板在搅拌的溶液中浸泡1、2、4和8小时。在每个间隔处,从每个溶液中拉出1个板并利用布擦拭以观看除去了多少粘合剂,如下表中所记录的。还使用45%d-苧烯/45%Steposol SB-W/10%Tomadol25-9的混合物进行了比较例。将结果示出在表14中。
表14
运行 | 溶剂 | 洗涤循环(小时) | 观察结果 |
1A | EtLPK | 1 | 完全除去 |
1B | EtLPK | 2 | 完全除去 |
1C | EtLPK | 4 | 完全除去 |
1D | EtLPK | 8 | 完全除去 |
2A | d-苧烯/豆油酸甲酯 | 1 | 无擦除 |
2B | d-苧烯/豆油酸甲酯 | 2 | 略微软化但无擦除 |
2C | d-苧烯/豆油酸甲酯 | 4 | 略微软化但无擦除 |
2D | d-苧烯/豆油酸甲酯 | 8 | 略微软化但无擦除 |
在粘合剂的所有时间间隔处,EtLPK都进行得比d-苧烯/豆油酸甲酯/Tomadol溶液好。在利用d-苧烯/豆油酸甲酯浸泡8小时之后的最终膜显示最少脱层的标记,并且即使当刮擦时,仍难以从金属基底上除去。
实施例10
通过利用乳胶手套将粘合剂手动擦拭到4-英寸×1-英寸钢板上,并在室温下固化24小时将由Loctite(Henkel)制造的PowerGrab All-PurposeConstruction Adhesive涂布到板上。然后,使用在280rpm下旋转的搅拌棒在恒定搅拌下将经涂布的板浸渍到90wt%EtLPK和10wt%Tomadol25-9表面活性剂溶液的溶液中。将经涂布的板在搅拌的溶液中浸泡1、2、4和8小时。在每个间隔处,从每个溶液中拉出1个板并利用布擦拭以观看除去了多少粘合剂,如下表中所记录的。还使用45%d-苧烯/45%Steposol SB-W/10%Tomadol25-9的混合物进行了比较例。将结果示出在表15中。
表15
运行 | 溶剂 | 洗涤循环(小时) | 观察结果 |
A1 | EtLPK | 1 | 软化但无擦除 |
A2 | EtLPK | 2 | 软化但无擦除 |
A3 | EtLPK | 4 | 软化且25%擦除 |
A4 | EtLPK | 8 | 软化且35%擦除 |
B1 | d-苧烯/豆油酸甲酯 | 1 | 软化但无擦除 |
B2 | d-苧烯/豆油酸甲酯 | 2 | 软化但无擦除 |
B3 | d-苧烯/豆油酸甲酯 | 4 | 软化但无擦除 |
B4 | d-苧烯/豆油酸甲酯 | 8 | 软化且35%擦除 |
Et LPK/Tomadol溶液进行得与d-苧烯/豆油酸甲酯/Tomadol溶液类似。在两种情况下,粘合剂都足够软而可以刮除但是利用毛巾擦拭时不会脱落。
实施例11
对EtLPK和Steposol SB-W(豆油酸甲酯)比较它们除去蜡涂料的能力。将蜡(由Lundmark Wax制造的All-Wax Floor Wax)与颜料(Sid Richardson黑色颜料SR-630)合并并使用沙子研磨以分散黑色颜料。以1、2和3密耳(0.025、0.055和0.076mm)湿膜使用刮涂棒将着色的蜡溶液涂布在标准乙烯基地砖上并使其干燥过夜。然后将溶剂浸透到固定至16盎司(0.45kg)圆头锤的圆边的粗棉中。将锤子连接至以3英寸(7.6cm)冲程将锤子来回移动的电动机。计算双摩擦冲程的总数,直至白砖通过除去的黑色蜡显示出来。将结果示出在表16中。
表16
蜡厚度,密耳(mm) | 溶剂 | 双摩擦 |
1(0.025) | EtLPK | 14 |
2(0.055) | EtLPK | 20 |
3(0.076) | EtLPK | 24 |
1(0.025) | 去离子水 | 273 |
1(0.025) | d-苧烯 | 6 |
2(0.055) | d-苧烯 | 8 |
3(0.076) | d-苧烯 | 9 |
1(0.025) | 豆油酸甲酯 | 25 |
2(0.055) | 豆油酸甲酯 | 28 |
3(0.076) | 豆油酸甲酯 | 33 |
在相关实施例中,通过利用压舌板经由手在管中混合而将蜡(SCJohnson Paste Wax)与颜料(Sid Richardson黑色颜料SR-630)合并。使用毛巾以均匀的厚度将着色的蜡溶液涂布在砖上并使其干燥过夜。将溶剂浸透到固定至16盎司(0.45kg)圆头锤的圆边的粗棉中。将锤子连接至以3英寸(7.6cm)冲程将锤子来回移动的电动机。计算双摩擦冲程的总数,直至白砖通过除去的黑色蜡显示出来。将结果示出在表17中。
表17
运行 | 溶剂 | 双摩擦 |
1 | EtLPK | 18 |
2 | 去离子水 | 227 |
3 | d-苧烯 | 9 |
4 | Steposol SB-W | 26 |
表16和17中的结果显示,EtLPK在除去蜡时有效。
实施例12
使用EtLPK、d-苧烯和Steposol SB-W(豆油酸甲酯)进行松焦油沥青除去。通过加热至85℃将得自Jas Townsend and Son的松焦油沥青熔化并然后利用海绵刷涂布至载玻片。在冷却过夜之后,将得到的经涂布载玻片***到包含实验溶剂的烧杯中。在90和180分钟时除去载玻片并通过利用和不利用擦拭时的总残渣量来评价沥青除去。将结果示出在表18中。
表18
运行 | 溶剂 | 浸泡时间(分钟) | 观察结果 |
1 | EtLPK | 90 | 软化,50%除去 |
2 | d-苧烯 | 90 | 100%除去;无擦拭 |
3 | 豆油酸甲酯(Steposol SB-W) | 90 | 利用擦拭100%除去 |
4 | EtLPK | 180 | 利用擦拭100%除去 |
5 | d-苧烯 | 180 | 100%除去;无擦拭 |
6 | 豆油酸甲酯(Steposol SB-W) | 180 | 利用擦拭100%除去 |
在擦拭180分钟之后,LPK将沥青除去。
实施例13
通过将4-英寸×1-英寸(10.16cm×2.54cm)板浸渍到沥青密封层(Sealbest100沥青密封层)中并在70℃下固化2小时而将所述沥青密封层涂布到所述板上。然后,使用在280rpm下旋转的搅拌棒在恒定搅拌下将经涂布的板浸渍到90wt%EtLPK和10wt%Tomadol25-9表面活性剂溶液的溶液中。将经涂布的板在搅拌的溶液中浸泡1、2、4和8小时。在每个间隔处,从每个溶液中拉出1个板并利用布擦拭以观看除去了多少粘合剂。将结果示出在表19中。
表19
实验 | 溶剂 | 洗涤循环(小时) | 观察结果 |
1 | EtLPK | 1 | 10%除去 |
2 | EtLPK | 2 | 30%除去 |
3 | EtLPK | 4 | 60%除去 |
4 | EtLPK | 8 | 95%除去 |
在8小时之后,EtLPK-Tomadol25-9溶液除去了几乎所有沥青。
实施例14
对EtLPK和EtLGK评价它们从儿童塑料玩具上除去标签的能力。首先通过剥离同样会脱落的标签而除去标签。然后,将具有来自标签的残余粘合剂和纸的区域利用缩酮浸泡1分钟;然后利用毛巾对该区域进行擦拭以评价性能。
目视观察显示,当将EtLPK用作溶剂时,标签残渣易于完全除去。一些黄色表现在擦拭材料(rag)上,但是对塑料玩具没有损伤。
相反,目视观察显示,当将EtLGK用作除去组合物时,将纸除去,但是未将粘合剂残渣除去。
实施例15
下表示出了用于所示的各种应用的制剂的预期实施例。所述量以基于制剂的总重量的重量百分数(wt%)计。
通用剥离剂制剂
通用剥离剂制剂
涂鸦除去制剂
*ExxonMobil Corporation
涂鸦除去制剂
涂鸦除去制剂
涂鸦除去制剂
涂鸦除去制剂
Stepan Company
React-NTI,LLC
脱漆剂制剂
**The Dow Chemical Company
***Ashland,Inc.
脱漆剂制剂
**The Dow Chemical Company
手清洁剂凝胶制剂
Stepan Company
React-NTI,LLC
焦油/沥青除去剂气溶胶制剂
部件洗涤剂制剂
Stepan Company
发动机脱脂制剂
地板乳香除去剂制剂
Stepan Company
混凝土油渍除去剂制剂
Stepan Company
本文中所用的术语仅是为了描述特定的实施方式的目的且不旨在为限制性的。如本文中所用的,单数形式“一个”、“一种”、以及“该”旨在包括所指对象的复数,除非在上下文中明确地表明不是这样。还应进一步理解,当用于本说明书中时,术语“包含”和/或“包括”或“含有”和/或“含”规定所述特征、区域、整数、步骤、操作、要素和/或成分的存在,但不排除一种或多种其他特征、区域、整数、步骤、操作、要素、成分和/或其组的存在或添加。涉及相同的成分或性质的所有范围的端点都将端点包括在内并可以独立地组合。
除非另有其他限定,否则本文中使用的所有术语(包括技术和科学术语)的含义与本发明所属领域的普通技术人员通常理解的含义相同。术语“油漆”包括还已知为例如真漆、电泳漆、虫漆、面漆、底漆、彩涂层等的任何外部保护涂料。术语“除去剂”包括清洁、点清洁和剥除的组合物,且“除去”包括清洁、点清洁和剥除。
在实施方式中,通过上述方法制备的化合物具有一种或多种异构体。在可以存在异构体的情况下,应理解,本发明包括形成其异构体的方法,所述异构体包括任何立体异构体、任何构象异构体和任何顺式、反式异构体;其分离的异构体;以及它们的混合物。
使用标准命名法描述化合物。例如,未被任何指示基团取代的任何位置被理解为具有由所示出的键或氢原子填充的其化合价。不在两个字母或符号之间的破折号(“-”)用于指示取代基的连接点。例如,-CHO通过羰基基团的碳连接。烷基基团可以是直链或支链的。在整个说明书中,提及了各种二价基团。这种基团与类似命名的单价基团相同且通常以“亚”前缀指示。例如,C1至C6亚烷基基团是具有与C1至C6烷基基团相同的结构的二价连接基团。
通过参考将所有引用的专利、专利公开和其他文献整体并入本文中。
上述各种实施方式仅通过例示性方式提供且不应被解释为限制所附的权利要求书。本发明可以适当地包含任何所公开的或所述的要素,由其组成或者基本由其组成。由此,本文中例示公开的本发明可以在不存在本文中未具体公开的任何要素的情况下适当地实践。可以意识到各种修改和变化,其可以在不遵循本文中说明和描述的示例性实施方式和用途并且不背离所附权利要求书的真实主旨和范围的情况下完成。
Claims (33)
1.一种除去组合物,包含:
多个磨料颗粒、有机胺、抗氧化剂、杀菌剂、增效剂、螯合剂、着色剂、腐蚀抑制剂、共溶剂、消泡剂、染料、酶、润湿剂、水溶助剂、无机碱、光稳定剂、遮味剂、pH调节剂、增塑剂、防腐剂、防锈剂、表面活性剂、增稠剂、或包含上述中的至少一种的组合;
基于所述除去组合物的总重量,0至1%水;和
式(1)的缩酮加合物:
其中,
R1是C1-6烷基,
R2是氢或者C1-3烷基,
各个R3、R4和R5独立地为氢或者C1-6烷基,
R6和R7各自独立地为氢或者C1-6烷基,
a=2或3,以及
b=0或l。
2.根据权利要求1所述的除去组合物,其中,R1是C1-6烷基,R2是甲基,各个R3、R4和R5各自独立地为氢或者C1-3烷基,R6是氢或者C1-6烷基,R7是氢,a=2或3,以及b=0或l。
3.根据权利要求1所述的除去组合物,其中,R1是C1-4烷基,R2是甲基,R3是氢,R6是氢或者C1-3烷基,R7是氢,a=2,以及b=0。
4.根据权利要求1-3中任一项所述的除去组合物,其中,R1是C1-4烷基,R2是甲基,R3是氢,R6是氢、甲基或乙基,R7是氢,a=2,以及b=0。
5.根据权利要求1-3中任一项所述的除去组合物,其中,所述缩酮加合物由式(la)表示:
其中,R1为C1-4烷基。
6.根据权利要求5所述的除去组合物,其中,R1为乙基或丁基。
7.根据权利要求1-3中任一项所述的除去组合物,包含共溶剂。
8.根据权利要求7所述的除去组合物,其中,所述共溶剂是酰胺。
9.根据权利要求7所述的除去组合物,其中,所述共溶剂是亚砜。
10.根据权利要求1-3中任一项所述的除去组合物,包含酰胺或亚砜共溶剂和胺促进剂。
11.根据权利要求1-3中任一项所述的除去组合物,包含增稠剂。
12.根据权利要求1-3中任一项所述的除去组合物,包含1-甲基-2-吡咯烷酮、增稠剂和表面活性剂。
13.根据权利要求1-3中任一项所述的除去组合物,包含二甲基亚砜、增稠剂和表面活性剂。
14.根据权利要求1-3中任一项所述的除去组合物,其中,所述除去组合物为除漆剂、涂鸦除去剂、油墨除去剂、密封剂除去剂、粘合剂除去剂、乳香除去剂、光致抗蚀剂除去剂、蜡除去剂、沥青除去剂、混凝土清洁剂、模板清洁剂、模具清洁剂、手清洁剂、身体清洁剂、树液除去剂、油除去剂、油脂除去剂或它们的组合。
15.根据权利要求1-3中任一项所述的除去组合物,其中,所述除去组合物被配制为液体、浓缩物或气溶胶。
16.根据权利要求1-3中任一项所述的除去组合物,其中,所述除去组合物以擦拭布的形式使用,所述擦拭布为用凝胶或液体除去组合物浸渍的天然或合成布片。
17.一种制备根据权利要求1-16中任一项所述的除去组合物的方法,包括:
将多个磨料颗粒、有机胺、抗氧化剂、杀菌剂、增效剂、螯合剂、着色剂、腐蚀抑制剂、共溶剂、消泡剂、染料、酶、润湿剂、水溶助剂、无机碱、光稳定剂、遮味剂、pH调节剂、增塑剂、防腐剂、防锈剂、表面活性剂、增稠剂、或包含上述中的至少一种的组合与式(1)的所述缩酮加合物合并。
18.根据权利要求17所述的方法,其中,所述pH调节剂为pH缓冲剂。
19.一种除去基材表面上的材料的方法,包括:
在除去条件下使基材表面上的材料与除去组合物接触,所述除去组合物包含:
基于所述除去组合物的总重量,0至1%水,和
式(1)的缩酮加合物:
其中,
R1是C1-6烷基,
R2是氢或者C1-3烷基,
各个R3、R4和R5独立地为氢或者C1-6烷基,
R6和R7各自独立地为氢或者C1-6烷基,
a=2或3,和
b=0或l;以及
将所述材料与所述基材至少部分分离。
20.根据权利要求19所述的方法,其中,R1是C1-6烷基,R2是甲基,各个R3、R4和R5各自独立地为氢或者C1-3烷基,R6是氢或者C1-6烷基,R7是氢,a=2或3,以及b=0或l。
21.根据权利要求19所述的方法,其中,R1是C1-4烷基,R2是甲基,R3是氢,R6是氢或者C1-3烷基,R7是氢,a=2,以及b=0。
22.根据权利要求19-21中任一项所述的方法,其中,R1是C1-4烷基,R2是甲基,R3是氢,R6是氢、甲基或乙基,R7是氢,a=2,以及b=0。
23.根据权利要求19-21中任一项所述的方法,其中,所述缩酮加合物由式(la)表示:
其中,R1为C1-4烷基。
24.根据权利要求23所述的方法,其中,R1为乙基或丁基。
25.根据权利要求19-21中任一项所述的方法,其中,所述除去组合物还包括多个磨料颗粒、有机胺、抗氧化剂、杀菌剂、增效剂、着色剂、腐蚀抑制剂、共溶剂、消泡剂、染料、酶、光稳定剂、遮味剂、增塑剂、防腐剂、防锈剂、表面活性剂、增稠剂、或包含上述中的至少一种的组合。
26.根据权利要求25所述的方法,其中,所述除去组合物包含共溶剂。
27.根据权利要求26所述的方法,其中,所述共溶剂是酰胺。
28.根据权利要求26所述的方法,其中,所述共溶剂是亚砜。
29.根据权利要求25所述的方法,其中,所述除去组合物包含酰胺或亚砜共溶剂和胺促进剂。
30.根据权利要求25所述的方法,其中,所述除去组合物包含增稠剂。
31.根据权利要求25所述的方法,包含1-甲基-2-吡咯烷酮、增稠剂和表面活性剂。
32.根据权利要求25所述的方法,包含二甲基亚砜、增稠剂和表面活性剂。
33.根据权利要求19-21中任一项所述的方法,其中,所述方法包括除去油漆、涂鸦、油墨、密封剂、粘合剂、乳香、光致抗蚀剂、模具残渣、模板残渣、蜡、沥青、树液、油、油脂或包含上述中的至少一种的组合。
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- 2011-08-12 US US13/208,797 patent/US8828917B2/en active Active
- 2011-08-12 KR KR1020137002649A patent/KR20130102532A/ko not_active Application Discontinuation
- 2011-08-12 EP EP11817119.8A patent/EP2603836A4/en not_active Withdrawn
- 2011-08-12 CN CN201180038383.6A patent/CN103069343B/zh not_active Expired - Fee Related
- 2011-08-12 JP JP2013524249A patent/JP5805764B2/ja active Active
- 2011-08-12 BR BR112013003424A patent/BR112013003424A2/pt not_active Application Discontinuation
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Also Published As
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AU2011289224A1 (en) | 2013-01-10 |
EP2603836A4 (en) | 2017-08-02 |
WO2012021824A2 (en) | 2012-02-16 |
AU2011289224B2 (en) | 2015-04-16 |
JP2013539487A (ja) | 2013-10-24 |
EP2603836A2 (en) | 2013-06-19 |
KR20130102532A (ko) | 2013-09-17 |
BR112013003424A2 (pt) | 2016-08-02 |
US20120040880A1 (en) | 2012-02-16 |
CA2803389A1 (en) | 2012-02-16 |
US8828917B2 (en) | 2014-09-09 |
JP5805764B2 (ja) | 2015-11-10 |
CA2803389C (en) | 2016-10-11 |
CN103069343A (zh) | 2013-04-24 |
WO2012021824A3 (en) | 2012-05-03 |
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