EP2013278A1 - Utilisation de composes hexahydrophthalimide comme plastifiants - Google Patents

Utilisation de composes hexahydrophthalimide comme plastifiants

Info

Publication number
EP2013278A1
EP2013278A1 EP07728373A EP07728373A EP2013278A1 EP 2013278 A1 EP2013278 A1 EP 2013278A1 EP 07728373 A EP07728373 A EP 07728373A EP 07728373 A EP07728373 A EP 07728373A EP 2013278 A1 EP2013278 A1 EP 2013278A1
Authority
EP
European Patent Office
Prior art keywords
ethyl
alkyl
pvc
carbon atoms
hexahydrophthalimide
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.)
Withdrawn
Application number
EP07728373A
Other languages
German (de)
English (en)
Inventor
Klemens Massonne
Boris Breitscheidel
Jürgen Holzmann
Axel Salden
Klaus Rossato
Martina Egen
Detlef Kratz
Lucien Thil
Jan-Dirk Arndt
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP07728373A priority Critical patent/EP2013278A1/fr
Publication of EP2013278A1 publication Critical patent/EP2013278A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/44—Iso-indoles; Hydrogenated iso-indoles
    • C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
    • 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
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C08K5/3417—Five-membered rings condensed with carbocyclic rings
    • 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
    • C08L27/06—Homopolymers or copolymers of vinyl chloride

Definitions

  • the invention relates to the use of certain hexahydrophthalimide compounds as plasticizers for thermoplastic polymers, in particular for polyvinyl chloride, and a molding composition containing at least one particular hexahydrophthalimide compound.
  • Polyvinyl chloride is one of the most widely used thermoplastic polymers. It is flame retardant, resistant to chemicals and corrosion resistant. The properties of PVC can be varied with the help of plasticizers within wide limits. Depending on the amount of plasticizer, a distinction is made between rigid PVC (less than 3% plasticizer) and soft PVC (more than 3% plasticizer).
  • the preferred softening agents are phthalic acid esters, in particular di-n-butyl phthalate (DBP), diisobutyl phthalate (DIBP), D-2-ethylhexyl phthalate (DEHP), diisononyl phthalate (DINP), diisodecyl phthalate (DIDP) and benzyl butyl phthalate (BBP ).
  • DBP di-n-butyl phthalate
  • DIBP diisobutyl phthalate
  • DEHP D-2-ethylhexyl phthalate
  • DINP diisononyl phthalate
  • DIDP diisodecyl phthalate
  • BBP benzyl butyl phthalate
  • esters of adipic acid and other organic acids as well as esters of phosphoric acid.
  • phthalates have a low acute toxicity. With chronic intake, DEHP can exert harmful effects on the testes, kidneys and liver even in small quantities. In animal studies DEHP impaired the reproductive ability and led to disorders of the sex organs of male offspring. A new risk assessment is currently underway in the European chemicals program. Since 1999 certain phthalates may no longer be present in toys. In addition to DEHP, these include the phthalates DINP, DBP, DIDP and BBP.
  • Gelling behavior is the ability of a plasticizer to penetrate the polymeric structure of the PVC and to cause a softening effect by reducing the interactions between the polymer chains.
  • a measure of the gelling behavior of a plasticizer is the dissolution temperature for PVC, which is determined according to DIN 53408. The lower the dissolution temperature, the better the gelling behavior.
  • the processing temperatures can be chosen lower in the production of flexible PVC, the better the gelling behavior or the lower the dissolving temperature of the plasticizer. Low temperatures lead to energy and time savings.
  • JP 63 301864, US-A 3652312, US-A 3615793, US-A 3579363, US-A 2547542, US-A 2684917, DE 860864, US-A 3579364, US-A 3957862, US-A 2547495 disclose the use of N Substituted phthalimides as plasticizers for various plastics.
  • US Pat. No. 3,210,313 describes ⁇ -dicarboximido-caproic acid esters, such as ⁇ -pthalimidocaproic acid ester, ⁇ -tetrahydrophthalimido-caproic acid ester and ⁇ -hexahydrophthalimido-caproic acid ester, as plasticizer for PVC.
  • Phthalimides have high dissolution temperatures for PVC. Tetrahydrophthalimides have olefinic double bonds and are therefore sensitive to oxidation and tend to yellow.
  • the invention is based on the object of providing alternative plasticizers and softened molding compositions.
  • the invention is directed to easy to produce plasticizers with good gelling behavior and low dissolution temperature for PVC.
  • the object is achieved by a molding composition which contains a thermoplastic polymer and at least one hexahydrophthalimide compound of the formula (I),
  • R is alkyl, cycloalkyl or cycloalkylalkyl, where the latter two radicals may be unsubstituted or substituted by alkyl, and the radical R has at least 6 carbon atoms.
  • the invention also relates to the use of a hexahydrophthalimide compound of the formula (I) as a plasticizer for polyvinyl chloride.
  • alkyl includes saturated, linear or branched hydrocarbon radicals, which generally have from 1 to 40 carbon atoms (C 1 -C 4 -alkyl), and are preferably straight-chain or branched alkyl groups.
  • Examples include C 1 -C 6 -alkyl, for example methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1, 1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl , 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1, 1-dimethylpropyl, 1, 2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1 , 2-Dimethylbutyl, 1, 3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1, 1, 2-trimethylpropyl, 1, 2,2 Trimethylpropyl, 1-ethy
  • C 1 -C 4 -alkyl examples are C 1 -C 6 -alkyl as mentioned above, and heptyl, 1-methylhexyl, 2-methylhexyl, 3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 1-ethylpentyl, 2-ethylpentyl, 3-ethylpentyl , 1-propylbutyl, 1, 1-dimethylpentyl, 1, 2-dimethylpentyl, 1, 3-dimethylpentyl, 1, 4-dimethylpentyl, 1-methyl-2-ethylbutyl, 1-ethyl-2-methylbutyl, 1-ethyl-1 -methylbutyl, octyl, 1-methylheptyl, 2-methylheptyl, 3-methylheptyl, 4-methylheptyl, 5-methylheptyl, 6-methylheptyl, 1-ethylhexyl, 2-ethylhexyl
  • cycloalkyl embraces monocyclic, saturated hydrocarbon groups which usually contain from 3 to 14 carbon atoms as ring members, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, cyclotridecyl and
  • cycloalkyl may be monosubstituted or polysubstituted, for example mono-, di-, tri-, tetra-, penta- or hexadiene, by alkyl, for example Ci-C ⁇ -alkyl, examples include 2-, 3 -Methylcyclopentyl, 2,2-dimethylcyclopentyl, 2,5-dimethylcyclopentyl, 4-
  • cycloalkylalkyl denotes an alkyl radical as defined above which is replaced by one or more monocyclic, saturated hydrocarbon groups which generally contain 3 to 14 carbon atoms as ring members, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl,
  • the cycloalkyl moiety may be monosubstituted or polysubstituted, for example mono-, di-, tri-, tetra-, penta- or trisubstituted, by alkyl, for example C.sub.1-4-cyclohexanediyl, cyclododecyl, cyclotridec
  • R is branched alkyl having 6 to 28 carbon atoms, in particular branched C7-C15-alkyl.
  • the alkyl radical may have one or more branches, in particular one or two branches, particularly preferably one branch.
  • the branches are preferably methyl, ethyl or n-propyl branches.
  • R is C 7 -C 15 -alkyl having a branch on the ⁇ -carbon atom, such as 2-ethylpentyl, 2-ethylhexyl, 2-propylpentyl, 2-ethylheptyl, 2-propylhexyl, 2-ethyloctyl , 2-propylheptyl, 2-ethylnonyl or 2-propyloctyl.
  • R is iso-alkyl having 8 to 28 carbon atoms, in particular 9 to 20 or 10 to 18 carbon atoms, eg. B. 8, 9, 10 or 13 carbon atoms, and a mean degree of branching of 1, 1 to 3.0, in particular 1, 5 to 2.5.
  • These include isooctyl, isononyl, isodecyl, isoundecyl, isododecyl and isotridecyl.
  • the isoalkyl radicals are usually derived from primary alcohols obtained by oligomerization of C 2 -C 6 olefins and subsequent hydroformylation and hydrogenation.
  • Preferably used hexahydrophthalimide compound have a vapor pressure at 200 ° C of less than 30 hPa, in particular less than 25 hPa.
  • the compounds of formula I can be prepared in many ways by literature methods, see Beilstein, Springer Verlag 1989, 5th. Suppl. Series EV 21/10 Page 78ff.
  • the compounds of the formula I can be prepared, for example, by reacting cyclohexanedicarboxylic acid or cyclohexanedicarboxylic anhydride with a primary amine R-NH.sub.2.
  • a primary amine R-NH.sub.2 a primary amine
  • aliphatic, cycloaliphatic or aromatic hydrocarbons such as hexane, cyclohexane, toluene, xylene, mesitylene or mixtures are used as solvents for these reactions this solvent.
  • the water of reaction is removed, for example by circling.
  • Cyclohexanedicarboxylic acid (anhydride) can be obtained by the process described in WO 02/066412.
  • Thermoplastic polymers which can be mixed with the plasticizers used according to the invention are, in addition to PVC, also polyvinyl acetals, such as polyvinyl butyral, polyacrylates, cellulose esters, in particular nitrocellulose and cellulose acetate, and polysulfides.
  • the content of compounds of the formula (I) - stated in phr - in the molding compositions of the invention may generally be from 5 to 100 phr, preferably from 10 to 60 phr and more preferably from 20 to 50 phr.
  • the formulation recipe "phr" common for polymer compositions is the abbreviation for "parts per hundred resin” and means that additives are not weighed, measured and reported in terms of their percentage in the total mass, but as parts by weight per 100 parts by weight of polymer. For example, if the compound of formula (I) is present in the PVC / plasticizer mixture in the weight ratio PVC: plasticizer of 80:20, the content of ester mixture is 25 phr, since 20 parts make up 25% of 80 parts.
  • Polyvinyl chloride is obtained by homopolymerization of vinyl chloride.
  • the polyvinyl chloride (PVC) used in the present invention can be prepared by, for example, suspension polymerization, microsuspension polymerization, emulsion polymerization or bulk polymerization.
  • the production of PVC by polymerization of vinyl chloride and the preparation and composition of plasticized PVC are described, for example, in "Becker / Braun, Kunststoff-Handbuch, Volume 2/1: Polyvinyl chloride", 2nd edition, Carl Hanser Verlag, Kunststoff.
  • the K value which characterizes the molar mass of the PVC and is determined in accordance with DIN 53726, is usually between 57 and 90, preferably between 61 and 85, in particular between 64 and 75, for the PVC softened according to the invention.
  • the molding composition according to the invention may contain other suitable additives in addition to the imidazole compound.
  • stabilizers for example, stabilizers, lubricants, fillers, pigments, flame retardants, light stabilizers, blowing agents, polymeric processing aids, impact modifiers, optical brighteners, antistatic agents or biostabilizers may be included.
  • additives and their function will be described below by way of example, without these statements having a limiting effect on the molding composition according to the invention.
  • Stabilizers for example, neutralize the hydrochloric acid split off from PVC during and / or after processing, or counteract PVC degradation as free-radical scavengers.
  • Suitable stabilizers are all customary stabilizers in solid and liquid form, for example customary Ca / Zn, Ba / Zn, Pb or Sn stabilizers and also acid-binding phyllosilicates such as hydrotalcite. Preference is given to Ba / Zn stabilizers, tribasic lead sulfate (3 PbO * PbSO 4 * H 2 O) and lead phosphite, particularly preferably tribasic lead sulfate and lead phosphite. Radical scavengers exemplified dibutyltin maleate.
  • the molding compositions according to the invention may have a content of stabilizers of from 0.05 to 7 phr, preferably from 0.1 to 5 phr and more preferably from 0.2 to 4 phr.
  • Lubricants are said to act between PVC particles and the hot machine parts during processing, and to counteract frictional forces associated with mixing, plasticizing and deforming.
  • the molding compositions according to the invention may contain all the lubricants customary for the processing of thermoplastic polymers, in particular of PVC.
  • lubricants customary for the processing of thermoplastic polymers, in particular of PVC.
  • hydrocarbons such as oils, paraffins and polyethylene waxes, fatty acid salts, fatty alcohols having 10 to 20 carbon atoms, ketones, carboxylic acids, such as fatty acids and montanic acid, oxidized polyethylene wax, metal salts of carboxylic acids, carboxylic acid amides and carboxylic acid esters, for example, with the alcohols ethanol, fatty alcohols, glycerol, ethanediol, pentaerythritol and long-chain carboxylic acids as the acid component.
  • the molding compositions according to the invention may have a lubricant content of from 0.01 to 10 phr, preferably from 0.05 to 5 phr and more preferably from 0.1 to 3 phr.
  • fillers have a positive influence on the compressive, tensile and flexural strength as well as the hardness and heat resistance of plasticized polyvinyl chloride.
  • Fillers for example inorganic fillers, such as natural calcium carbonates, for example chalk, limestone and marble, synthetic calcium carbonates, dolomite, silicates, silicic acid, sand, diatomaceous earth, aluminum silicates, such as kaolin, mica and feldspar, can be added to the molding compositions according to the invention.
  • Preference is given to using calcium carbonates, chalk, dolomite, kaolin, silicates or talc as fillers, particularly preferably chalk or calcite.
  • compositions of the invention may have a content of fillers of 0.01 to 100 phr and preferably 1 to 80 phr.
  • the molding compositions according to the invention may also contain pigments in order to adapt the product obtained to different possible uses.
  • inorganic pigments and organic pigments can be used for this purpose.
  • inorganic pigments for example, titanium pigments such as TiO 2, cobalt pigments such as COO / Al 2 O 3, and chromium (III) pigments such as Cr 2 O 3 may be used.
  • Suitable organic pigments are, for example, condensed azo pigments, azomethine pigments, anthraquinone pigments, quinacridones, phthalocyanine pigments, dioxazine pigments, for example Cl. Pigment Violet 23 and aniline black (CI Pigment Black 1) into consideration.
  • the molding compositions according to the invention may have a content of pigments of from 0.01 to 10 phr, preferably from 0.05 to 5 phr, more preferably from 0.1 to 3 phr and in particular from 0.5 to 2 phr.
  • flame retardants can also be added to the molding compositions according to the invention.
  • antimony trioxide, phosphoric acid esters, chloroparaffin, aluminum hydroxide, boron compounds, molybdenum trioxide or ferrocene can be used as flame retardants.
  • the molding compositions according to the invention may have a content of flame inhibitors of from 0.01 to 100 phr and preferably from 0.1 to 20 phr.
  • light stabilizers can also be added to these PVC rock mixtures.
  • hydroxybenzophenones hydroxyphenylbenzotriazoles or cyanophenyl acrylates can be used for this purpose.
  • Cyanophenyl acrylates are preferred, more preferably 2-ethylhexyl-2-cyano-3,3-diphenylacrylate.
  • the molding compositions according to the invention may contain light stabilizers in an amount of from 0.01 to 7 phr, preferably from 0.1 to 5 phr and more preferably from 0.2 to 1 phr.
  • plasticized PVC using the plasticizers according to the invention is usually carried out by mixing the individual components with stirring at elevated temperatures.
  • the preparation of mixtures of polyvinyl chlorides, plasticizers and other additives is generally described for example in "Becker / Braun, Plastics Handbook, Volume 2/1: polyvinyl chloride", 2nd ed. Carl Hanser Verlag, Kunststoff.
  • the polyvinyl chloride and all other solid constituents are first prepared by stirring at a stirring speed of 500 to 5000 rpm (revolutions per minute), preferably 1000 to 3000 rpm, more preferably 2000 to 2500 rpm, at a temperature of 30 to 150 ° C, preferably 40 to 100 ° C, particularly preferably 50 to 70 ° C, mixed.
  • the plasticizers according to the invention and all further liquid constituents are added and mixed by stirring at a stirring speed of 500 to 5000 rpm (revolutions per minute), preferably 1000 to 3000 rpm, particularly preferably 2000 to 2500 rpm, the temperature being reduced to one End value of 70 to 190 ° C, preferably 80 to 160 ° C, particularly preferably 90 to 130 ° C, is increased. Subsequently, the mixture is cooled to room temperature and can be further processed to finished articles.
  • the plasticizers according to the invention are suitable, for example, for the production of PVC films.
  • the plasticizers according to the invention are particularly suitable for the production of self-adhesive films, automotive films, furniture and office supplies films, agricultural films, food films, roofing membranes, oil tank inner foils, water reservoir foils, pool foils, building protection foils, raincoats, swing doors, shower curtains, dinghies, water wings.
  • the plasticizers according to the invention are also suitable for the production of PVC cables.
  • the plasticizers according to the invention are particularly suitable for the production of installation cables, power cables, communication cables, helical cords, computer cables, automobile cables.
  • the plasticizers according to the invention are also suitable for the production of PVC coatings.
  • the plasticizers according to the invention are particularly suitable for the production of artificial leather (for use in automobile or tannery), truck and tarpaulins, tablecloths, protective clothing, vinyl wallpaper, conveyor belts.
  • the plasticizers according to the invention are also suitable for the production of PVC floor coverings.
  • the plasticizers according to the invention are particularly suitable for the production of foamed floor coverings (Cudhion vinyl), heterogeneous compact coverings, homogeneous compact coverings, and carpet floor coverings.
  • the plasticizers according to the invention are also suitable for the production of PVC profiles.
  • the plasticizers according to the invention are particularly suitable for the production of industrial hoses and garden hoses, seals (for use, for example, in refrigerators), medical hoses, staircase handrails.
  • the plasticizers of the present invention are also particularly useful in the manufacture of footwear, including boots and sandals, toys, including dolls and footballs, gloves, including industrial and medical gloves, underbody protection, end caps, bellows, erasers.
  • the preparation of these finished articles can be done by calendering, extrusion, coating, casting, dipping, Rotomoulding or injection molding. Further details on these processing methods can be found, for example, in "Becker / Braun, Kunststoff-Handbuch, Volume 2/1: Polyvinyl chloride", 2nd ed. Carl Hanser Verlag, Kunststoff.
  • the solution was shaken out five times with 200 ml of 2% strength sodium hydroxide solution, then washed twice with 200 ml of water and dried over potassium carbonate.
  • the solvent was distilled off on a rotary evaporator at a bath temperature of 60 ° C. in an oil pump vacuum.
  • the plasticizer according to the invention from Example 1 has a comparatively low dissolving temperature for PVC as the typical fast-gelling plasticizer diisobutyl phthalate, which is significantly lower than that of the standard plasticizer di (2-ethylhexyl) phthalate.
  • the vapor pressure of the plasticizer according to the invention is significantly lower over the entire relevant temperature range of 140 to 200 ° C than that of diisobutyl phthalate.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Indole Compounds (AREA)

Abstract

L'invention concerne l'utilisation de composés hexahydrophthalimide de formule (I) comme plastifiants pour masses moulées, en particulier en chlorure de polyvinyle, dans lesquels R désigne un groupe alkyle, cycloalkyle ou cycloalkylalkyle, les deux derniers radicaux cités étant non substitués ou pouvant être substitués par un groupe alkyle et le radical R présente au moins 6 atomes de carbone.
EP07728373A 2006-04-21 2007-04-20 Utilisation de composes hexahydrophthalimide comme plastifiants Withdrawn EP2013278A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP07728373A EP2013278A1 (fr) 2006-04-21 2007-04-20 Utilisation de composes hexahydrophthalimide comme plastifiants

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP06008297 2006-04-21
PCT/EP2007/053916 WO2007122204A1 (fr) 2006-04-21 2007-04-20 Utilisation de composes hexahydrophthalimide comme plastifiants
EP07728373A EP2013278A1 (fr) 2006-04-21 2007-04-20 Utilisation de composes hexahydrophthalimide comme plastifiants

Publications (1)

Publication Number Publication Date
EP2013278A1 true EP2013278A1 (fr) 2009-01-14

Family

ID=37137451

Family Applications (1)

Application Number Title Priority Date Filing Date
EP07728373A Withdrawn EP2013278A1 (fr) 2006-04-21 2007-04-20 Utilisation de composes hexahydrophthalimide comme plastifiants

Country Status (7)

Country Link
US (1) US20090149584A1 (fr)
EP (1) EP2013278A1 (fr)
JP (1) JP2009534495A (fr)
KR (1) KR20090009886A (fr)
CN (1) CN101426843A (fr)
CA (1) CA2648535A1 (fr)
WO (1) WO2007122204A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2274374B1 (fr) * 2008-05-07 2014-07-16 E. I. du Pont de Nemours and Company Plastifiants comprenant des esters de poly(triméthylène éther) glycol
JP5650930B2 (ja) * 2010-05-28 2015-01-07 住江織物株式会社 カーペット及びその製造方法
CN102140212B (zh) * 2011-04-07 2013-03-06 浙江盛丰塑胶有限公司 一种半硬质聚氯乙烯写真压延薄膜生产工艺
JP7336538B2 (ja) * 2019-12-02 2023-08-31 タキロンシーアイ株式会社 ブラスト工法用シート

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Publication number Priority date Publication date Assignee Title
US2547542A (en) * 1949-11-29 1951-04-03 Rohm & Haas Aromatic imido-esters production
US2684917A (en) * 1950-12-08 1954-07-27 Henkel & Cie Gmbh Softening, gelatinizing, and swelling agents and methods of manufacturing the same
US3210313A (en) * 1959-08-25 1965-10-05 Allied Chem Esters of epsilon-dicarboximido-caproic acids and polyvinyl resins plasticized therewith
DE1288787B (de) * 1966-09-08 1969-02-06 Bayer Ag Polyamidformmassen mit imidgruppenhaltigen Verbindungen als Entformungsmittel
US3579363A (en) * 1968-11-19 1971-05-18 Monsanto Co Plasticized resin compositions
US3615793A (en) * 1968-11-21 1971-10-26 Monsanto Co Bis (phthalimido) alkane plasticized resin compositions
US3579364A (en) * 1968-11-21 1971-05-18 Monsanto Co Plasticized resin compositions
US3652312A (en) * 1971-01-18 1972-03-28 Monsanto Co Phthalimide plasticizer and non-proteinaceous resin mix
US3957862A (en) * 1973-03-30 1976-05-18 General Electric Company Method of making aromatic bis(ether ortho phthalic acid)s
DE2705089C2 (de) * 1976-02-10 1986-12-11 Henkel KGaA, 4000 Düsseldorf Gleitmittel für die formgebende Verarbeitung thermoplastischer Kunststoffe
WO2002066412A1 (fr) * 2001-02-16 2002-08-29 Basf Aktiengesellschaft Procede de production d'acides cyclohexanedicarboxyliques et leurs derives

Non-Patent Citations (1)

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Title
See references of WO2007122204A1 *

Also Published As

Publication number Publication date
JP2009534495A (ja) 2009-09-24
US20090149584A1 (en) 2009-06-11
CN101426843A (zh) 2009-05-06
WO2007122204A1 (fr) 2007-11-01
KR20090009886A (ko) 2009-01-23
CA2648535A1 (fr) 2007-11-01

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