EP1523507A1 - Seitenkettenmodifizierte copolymerwachse - Google Patents

Seitenkettenmodifizierte copolymerwachse

Info

Publication number
EP1523507A1
EP1523507A1 EP03732502A EP03732502A EP1523507A1 EP 1523507 A1 EP1523507 A1 EP 1523507A1 EP 03732502 A EP03732502 A EP 03732502A EP 03732502 A EP03732502 A EP 03732502A EP 1523507 A1 EP1523507 A1 EP 1523507A1
Authority
EP
European Patent Office
Prior art keywords
chain
acrylic acid
long
tetramethylpiperidinol
alcohols
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Withdrawn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
EP03732502A
Other languages
German (de)
English (en)
French (fr)
Inventor
Franz-Leo Heinrichs
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.)
Clariant Produkte Deutschland GmbH
Original Assignee
Clariant GmbH
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 Clariant GmbH filed Critical Clariant GmbH
Publication of EP1523507A1 publication Critical patent/EP1523507A1/de
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/14—Esterification
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups

Definitions

  • the invention relates to side-chain-modified copolymer waxes made from long-chain olefins, acrylic acid esters, acrylic acid and / or acrylic acid amides, a process for their preparation and their use.
  • Copolymers with varying proportions of ethylene and acrylic acid are widely used. They are characterized by a high linear
  • side-chain-modified copolymer waxes of the type mentioned at the outset characterized in that they are produced from waxy copolymers of long-chain ⁇ -olefins with 18 to 60 carbon atoms, methyl acrylate, acrylic acid and / or acrylic acid amides, the carboxyl functionality of which is obtained by chemical reaction with nucleophilic ones Components was modified.
  • the nucleophilic components are preferably long-chain alcohols, perfluoroalkyl alcohols, short-chain amines, long-chain amines and / or amino alcohols.
  • the long-chain alcohols are preferably tallow fatty alcohol, coconut fatty alcohol, oxo alcohols and / or Guerbet alcohol.
  • the perfluoroalcohols are preferably C ⁇ -C-i ⁇ -perfluoroalkylpropanol and distillate cuts of these alcohols.
  • Distillate cut Distillation is a physical separation method in which the different boiling points of the constituents (components) of a mixture are used for the separation. In its simplest variant, the liquid dripping from the cooler is successively in small portions and caught separately. This process continues until most of the original volume has been distilled. The composition of the individual fractions is then examined using a suitable method. These fractions are also referred to as distillation cuts. The composition of these fractions depends on the boiling point differences of the individual components and the distillation conditions.
  • the short-chain amines are preferably butylamine, dimethylaminopropylamine, diethylaminoethanol, tetramethylpiperidinol and / or triacetone diamine.
  • the long-chain amines are preferably octylamine, decylamine, dodecylamine, tallow fatty amine, coconut fatty amine, didecylamine and / or cyclohexylamine.
  • long-chain compounds are usually understood to mean those with alkyl chain lengths> C8 as they occur in wetting agents, surfactants and waxes. Linear aliphatic as well as branched aliphatic and cycloaliphatic substances can fall under this term.
  • the alkanolamines are preferably diethylaminoethanol
  • the present object is also achieved by a process for the production of side-chain-modified copolymer waxes, characterized in that long-chain alpha-olefins having 18 to 60 C atoms are first reacted with acrylic acid esters, acrylic acid and / or acrylic acid amides to give long-chain copolymer waxes and then with nucleophilic components to the side chain modified copolymer waxes.
  • the nucleophilic components are preferably long-chain alcohols such as tallow fatty alcohol, coconut fatty alcohol, oxo alcohols and / or Guerbet alcohol; perfluoroalkyl alcohol such as C 8 -C 8 perfluoroalkyl propanol 'and distillate cuts of these alcohols; short-chain amines such as butylamine, dimethylaminopropylamine, diethylaminoethanol, tetramethylpiperidinol and / or triacetone diamine; to long-chain amines, such as octylamine, decylamine, dodecylamine, tallow fatty amine, coconut fatty amine, didecylamine and / or cyclohexylamine and / or to alkanolamines, such as diethylaminoethanol, 2,2,6,6-tetramethyl-piperidinol, N-methyl-2,2,6 ,
  • long-chain alcohols such as t
  • the invention also relates to the use of the side chain-modified copolymer waxes according to the invention in emulsified form for coatings and the water-repellent effect.
  • the side chain modified copolymer waxes are also used in micronized form as matting agents, slip agents, anti-scratch agents and to improve chemical resistance.
  • carboxyl functionality is explained as follows: When olefins are copolymerized with acrylic acid and acrylic acid esters, polymers are formed which contain carboxylic acid and ester functions. These functions are commonly referred to as carboxyl functions. In the raw materials, it is the functionality of the acid COOH and the methyl ester COOCH3 that are changed to COOR and CONR 1 R 2 in the reaction products according to the invention. Here R is to be understood as meaning alkyl groups which are not CH 3 .
  • Comparative Example 1 Copolymer of C3o- ⁇ -olefins with acrylic acid / acrylic acid methyl ester
  • the olefin is melted at 100 ° C., the batch is heated to 150 ° C., then di-tert-butyl ester, methyl acrylate and acrylic acid are metered in and the mixture is stirred for 5 hours. The free monomers are distilled off.
  • Acrylic acid methyl ester 1.5 mol of di-tert-butyl peroxide 5% by weight on acrylic acid methyl ester
  • the olefin is melted at 100 ° C., the mixture is heated to 150 ° C., then di-tert-butyl peroxide and methyl acrylate are metered in and the mixture is stirred for 3 hours. The free monomers are distilled off.
  • Acrylic acid methyl ester 2.5 mol of di-tert-butyl peroxide 5% by weight on acrylic acid methyl ester
  • the olefin is melted at 100 ° C., the batch is heated to 150 ° C., then di-tert-butyl peroxide and methyl acrylate are metered in and the mixture is stirred for 5 hours. The free monomers are distilled off.
  • Example 1 copolymer wax modified with tallow fatty alcohol side chains copolymer according to Comparative Example 3 1 mol
  • the copolymer is melted at 100 ° C., the catalyst (Na methylate) and the alcohol component (tallow fatty alcohol) are added and the mixture is heated to 180 ° C. At this temperature, the mixture is stirred for 7 hours and the methanol liberated is distilled off. Then vacuum is applied to distill off residues of methanol and other alcohols, it is neutralized with phosphoric acid, cooled to 120 ° C. and filtered.
  • Viscosity number (cm 3 / g): 80 Dropping point (° C): 74.3
  • the product is suitable as a lubricant for PVC with a light color and adjustable polarity via the degree of exchange, and as a dispersing aid for pigments
  • Copolymer wax modified with perfluoroalkylpropanol (Ci 2 -C . ) Side chains
  • the copolymer is melted at 100 ° C, mixed with the catalyst (Na methylate) and the alcohol component (Ci 2 -C ⁇ -perfluoroalkylpropanol) and heated to 180 ° C. At this temperature, the mixture is stirred for 7 hours and the liberated methanol is distilled off. Then vacuum is applied to distill off residues of methanol and other alcohols, it is neutralized with phosphoric acid, cooled to 120 ° C. and filtered.
  • the catalyst Na methylate
  • the alcohol component Ci 2 -C ⁇ -perfluoroalkylpropanol
  • the product is suitable for the production of emulsions with a water-repellent effect, car polishes, textile emulsions as well as for the production of micronisates with a particle size of approx. 10 microns and for the adjustment of gloss and slipperiness in aqueous and solvent-based paints.
  • Test wax according to Example 3 5.0 g
  • the copolymer is melted at 100 ° C., the catalyst ( ® Fascat 4102) and the amine component are added and the mixture is heated to 190 ° C. At this temperature, the mixture is stirred for 7 hours and the liberated methanol is distilled off. Then vacuum is applied to distill off residues of methanol and amine, it is cooled to 120 ° C. and filtered. Acid number: 10
  • Example 4 Triacetone diamine-modified chain wax-modified copolymer wax Copolymer according to Comparative Example 4 1 mol
  • the copolymer is melted at 100 ° C., the catalyst (/ ®Tc ascat 4102) and the amine component are added and the mixture is heated to 190 ° C. At this temperature, the mixture is stirred for 7 hours and the liberated methanol is distilled off. Then vacuum is applied in order to distill off residual methanol and amine, the mixture is cooled to 150 ° C. and filtered.
  • Viscosity number (cm 3 / g): 136 Drop point (° C): 120 ° C Alkali number: 67.8 Melt viscosity (170 ° C): 572 mPas
  • Example 5 Copolymer wax modified with 2,2,6,6-tetramethylpiperidinol side chain
  • the copolymer is melted at 100 ° C., the catalyst and the amine component are added and the mixture is heated to 190 ° C. At this temperature, the mixture is stirred for 7 hours and the methanol liberated is distilled off. Then vacuum is applied to distill off residues of methanol and amine, it is cooled to 150 ° C. and filtered.
  • the product is used as a processing aid in polypropylene with light protection.
  • the copolymer is melted at 100 ° C, the catalyst and the amine component are added and the mixture is heated to 190 ° C. At this temperature, the mixture is stirred for 7 hours and the methanol liberated is distilled off. Then vacuum is applied to distill off residues of methanol and amine, it is cooled to 150 ° C. and filtered. Acid number: 16
  • the copolymer is melted at 100 ° C., the catalyst and the amine component are added and the mixture is heated to 190 ° C. At this temperature, the mixture is stirred for 7 hours and the methanol liberated is distilled off. Then vacuum is applied to distill off residues of methanol and amine, it is cooled to 150 ° C. and filtered.
  • Wax emulsifier 2.25 g
  • the copolymer is melted at 100 ° C., the catalyst and the amine component are added and the mixture is heated to 190 ° C. At this temperature, the mixture is stirred for 7 hours and the methanol liberated is distilled off. Then vacuum is applied to distill off residues of methanol and amine, it is cooled to 150 ° C. and filtered.
  • Copolymers available according to the prior art are essentially based on reactions of ethylene or long-chain olefins with acrylic acid or acrylic acid esters.
  • these are plastics that cannot be modified further; in the case of long-chain olefins, they are waxy compounds.
  • special functionality is achieved by incorporating appropriate acrylic acid derivatives, for example stearyl acrylate, 2,2,6,6-tetramethylpiperidinyl acrylate, perfluoroalkyl acrylate, N-octylacrylamide, etc.
  • the chemical modification of waxy copolymers of long-chain olefins and acrylic acid compounds according to the present invention is more economical and easier to control in functionality.
  • the acrylic acid compound can be reacted with the desired functional components by carrying out the reaction appropriately.
  • Wax-like polymers can be produced in this way for a wide range of applications.

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
EP03732502A 2002-06-08 2003-05-30 Seitenkettenmodifizierte copolymerwachse Withdrawn EP1523507A1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10225652A DE10225652B4 (de) 2002-06-08 2002-06-08 Seitenkettenmodifizierte Copolymerwachse
DE10225652 2002-06-08
PCT/EP2003/005671 WO2003104289A1 (de) 2002-06-08 2003-05-30 Seitenkettenmodifizierte copolymerwachse

Publications (1)

Publication Number Publication Date
EP1523507A1 true EP1523507A1 (de) 2005-04-20

Family

ID=29594350

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03732502A Withdrawn EP1523507A1 (de) 2002-06-08 2003-05-30 Seitenkettenmodifizierte copolymerwachse

Country Status (6)

Country Link
US (1) US20060036013A1 (enExample)
EP (1) EP1523507A1 (enExample)
JP (1) JP2005529204A (enExample)
CN (1) CN1284803C (enExample)
DE (1) DE10225652B4 (enExample)
WO (1) WO2003104289A1 (enExample)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1681046A3 (de) * 2004-11-13 2008-07-30 Clariant Produkte (Deutschland) GmbH Kosmetische, pharmazeutische und dermatologische Zubereitungen enthaltend Copolymerwachse
DE102005007980A1 (de) * 2005-02-22 2006-02-23 Clariant Gmbh Kosmetische, pharmazeutische oder dermatologische Zubereitungen enthaltend Copolymerwachse
ES2340903A1 (es) * 2008-09-22 2010-06-10 Repsol Ypf, S.A. Pelicula polimerica, procedimiento de obtencion y usos de la misma.
DE102009013902A1 (de) * 2009-03-19 2010-09-23 Clariant International Limited Verwendung von Copolymerisaten als Additive für Lacke
DE102011014250A1 (de) * 2011-03-17 2012-09-20 Clariant International Ltd. Pulverlackzusammensetzung zum Strukturieren und Texturieren von Lackoberflächen
CN115141547B (zh) * 2022-06-01 2023-04-11 科顺防水科技股份有限公司 非固化防水涂料及其制备方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL251563A (enExample) * 1959-05-15
US4413096A (en) * 1981-04-13 1983-11-01 Ciba-Geigy Corporation α-Olefin copolymers containing pendant hindered amine groups
US4885325A (en) * 1985-07-13 1989-12-05 Sandoz Ltd. Water dispersible quaternized aminoamide-modified waxes useful as textile finishing agents
CH669956A5 (enExample) * 1985-07-13 1989-04-28 Sandoz Ag
DE4139601C2 (de) * 1991-11-30 1994-09-08 Hoechst Ag Copolymerisate und ihre Verwendung als Gleit- und Trennmittel für die Verarbeitung thermoplastischer Kunststoffe
AU2001247267A1 (en) * 2000-03-30 2001-10-15 E.I. Du Pont De Nemours And Company Process for crosslinking of ehtylene/acrylic ester copolymers
FR2826454B1 (fr) * 2001-06-26 2003-10-17 Bio Merieux Cartes d'analyse

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO03104289A1 *

Also Published As

Publication number Publication date
WO2003104289A1 (de) 2003-12-18
DE10225652A1 (de) 2003-12-24
DE10225652B4 (de) 2004-10-28
CN1284803C (zh) 2006-11-15
CN1659191A (zh) 2005-08-24
US20060036013A1 (en) 2006-02-16
JP2005529204A (ja) 2005-09-29
HK1079226A1 (en) 2006-03-31

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