WO2020244485A1 - Modificateurs d'impact à basse température ayant une bonne transparence et une bonne résistance aux intempéries - Google Patents

Modificateurs d'impact à basse température ayant une bonne transparence et une bonne résistance aux intempéries Download PDF

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Publication number
WO2020244485A1
WO2020244485A1 PCT/CN2020/093801 CN2020093801W WO2020244485A1 WO 2020244485 A1 WO2020244485 A1 WO 2020244485A1 CN 2020093801 W CN2020093801 W CN 2020093801W WO 2020244485 A1 WO2020244485 A1 WO 2020244485A1
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Prior art keywords
core
shell
polymer
latex
sebazate
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Ceased
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PCT/CN2020/093801
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English (en)
Inventor
Michael Schiller
Qing YAN
Yifeng YAN
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Shenzhen Aimsea Industrial Co Ltd
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Shenzhen Aimsea Industrial Co Ltd
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Priority to CN202080041498.XA priority Critical patent/CN114174386A/zh
Publication of WO2020244485A1 publication Critical patent/WO2020244485A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • 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
    • C08F285/00—Macromolecular compounds obtained by polymerising monomers on to preformed graft polymers

Definitions

  • the invention relates to the field of impact modifiers, more specifically, to impact modifiers for low temperature applications with good transparency and weatherability.
  • Impact modifiers are crucial additives for many applications and plastics, especially for PVC window profiles and in some regions even for pipes.
  • Impact resistance or impact strength is defined as "the ability of a material or structure made of it to withstand the application of a sudden load without failure. "
  • PVC as a pure polymer already has good impact strength. In some cases, however, it is necessary to improve the impact resistance by adding impact modifiers.
  • the impact resistance of the PVC end product depends on many factors, e.g. on temperature.
  • Core-shell impact modifiers based on acrylate are produced by emulsion polymerization with radical initiators [S. -K. Ko; “Dar ein von Core-Shell Polymeren mit Spotify polymerer Azo-Initiatoren “ (Synthesis of core-shell polymers with the aid of polymeric azo initiators) , H. Utz Verlagtician, Germany H. Utz Verlagmaschine, Germany (1998) p. 10] . Suitable monomers are combined and polymerized in several steps. Crosslinking agents are added to form the crosslinked rubbery phase of the core, which generally has a glass transition temperature Tg of about -45°C and above. They are characterized by good properties in terms of impact resistance, transparency and weatherability.
  • Methyl methacrylate (MMA) butadiene styrene modifiers also have a core-shell structure. As the name suggests, they are made by copolymerizing styrene, butadiene and MMA, which are present in the shell analogously to the AIMs.
  • the glass transition temperature Tg of MBS types is significantly lower than that of AIMs. They are at -55°C [DE 2726256 C2] and below (up to -70°C [Technical information-Clearstrength E-920; http: //www. arkema-inc. com/tds/1325. pdf; downloaded (03/2014) ] ) .
  • the MBS modifiers are therefore perfect for low temperature applications. However, they have a negative impact on transparency and are not suitable for outdoor applications that require weatherability.
  • core-shell modifiers which contain crosslinked silicones in the core are also to be mentioned in this context [US5969045] . They combine good weatherability with a very low glass transition temperature Tg, which is significantly lower than that of AIMs.
  • the purpose of the present invention is providing impact modifiers for low temperature applications with good transparency and weatherability.
  • Graft copolymer with core-shell structure characterized in that the core is produced by several steps of a successive emulsion polymerization of one or more monomers in the presence of one or more plasticizers, the plasticizer content being 10 to 80%and the monomer content being 90 to 10%.
  • Graft copolymer with core-shell structure characterized in that the monomers are selected from the group C1-C12-alkyl acrylates, C1-C12-alkyl methacrylates, styrene and its substituted derivatives as well as vinyl ethers, vinyl esters or vinyl propionate
  • Graft copolymer with core-shell structure characterized in that the plasticizers are selected from the group consisting of azelate, phenyl alkylsulfonic acid, azelates, benzoates, chlorinated paraffins, citrates, epoxies, ricinolates, phosphates, valerates, phthalates, sebacates, terephthalates and trimellitates.
  • the plasticizers are selected from the group consisting of azelate, phenyl alkylsulfonic acid, azelates, benzoates, chlorinated paraffins, citrates, epoxies, ricinolates, phosphates, valerates, phthalates, sebacates, terephthalates and trimellitates.
  • the plasticizers are selected from the group dibutyl adipate, di (2-ethylhexyl) adipate, di-decyl adipate, di-i-nonyl adipate, di-i-octyl adipate, di-i-tridecyl adipate, Di-n-octyl adipate, dibutylazelate, di (2-ethylhexyl) azelate, di-decylazelate, di-i-nonylazelate, di-i-octylazelate, di-i-tridecylazelate, di-n-octylazelate, dibutyl sebazate, di (2-ethylhexyl) sebazate, di-decyl sebazate, di-i-nonyl sebazate, di-i-nonyl sebazate, di-i-n
  • b. are predominantly formed from units derived from methyl methacrylate
  • a. are predominantly formed from units derived from methyl methacrylate
  • Method comprises the final core-shell polymer is isolated by (a) spray drying or (b) coagulating, preferably by adding an aqueous solution of an inorganic acid salt.
  • thermoplastic resin comprising:
  • thermoplastic resin optionally processed into an article by extrusion, calendering or injection molding.
  • thermoplastic resin is a homo-or copolymer of vinyl chloride, a chlorinated PVC or a homo-or copolymer of methyl methacrylate or a technical resin such as a polyester of terephthalic acid and an aliphatic glycol, a polyamide, a polycarbonate B. a polyglutarimide, an acrylonitrile-butadiene-styrene resin or a mixture of at least two such resins.
  • Mixture comprising 60 to 99%by weight of a thermoplastic polymer and 1 to 40%by weight of the core-shell graft copolymer or produced by a process.
  • Mixture further contains one or more constituents: lubricant, processing aid, rheology modifier, dye, pigment, flame retardant, heat stabilizer, antioxidant, antiozonant, ultraviolet stabilizer, mold release agent, reinforcing or non-reinforcing filler.
  • Subject of the recent invention is to provide a silicone-free impact modifier which has good weatherability, good transparency and good impact strength at low temperatures ( ⁇ -50°C. ) .
  • a suitable plasticizer in the core it is possible to reduce the glass transition temperature Tg of the impact modifiers based on acrylates, to maintain the transparency and weathering properties and thereby to increase the impact strength at low temperatures.
  • Examples of the monomers used are based on styrene and acrylic acid derivatives.
  • alkyl acrylates are the C1-C12 alkyl acrylates, e.g. Methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, are of particular importance.
  • Suitable vinyl aromatic monomers are styrene and its mono-or polysubstituted derivatives, for example 4-methylstyrene, 4-ethylstyrene, 4-isopropylstyrene, 3, 4-dimethylstyrene, 4-chlorostyrene, 4-bromostyrene, 3, 4-dichlorostyrene. Styrene is particularly preferred.
  • Other monomers can e.g. vinyl ethers such as vinyl isobutyl ether and vinyl esters such as vinyl acetate or vinyl propionate or C1-C8 alkyl methacrylates. The use of further monomers is not absolutely necessary to improve the impact resistance and transparency, but can be advantageous in some cases.
  • Crosslinking di-or polyunsaturated monomers are e.g. allyl, methallyl and vinyl esters of di-, tri-or higher carboxylic acids such as e.g. adipic acid divinyl ester, phthalic acid diallyl ester, maleic acid diallyl ester, fumaric acid diallyl ester; Allyl, methallyl and vinyl ethers of polyfunctional alcohols such as ethylene glycol divinyl ether, 1, 3-butadiene diol divinyl ether, 1, 4-butanediol divinyl ether, pentaerythritol triallyl ether; esters of acrylic or methacrylic acid with polyhydric alcohols such as ethylene glycol di (meth) acrylate, 1, 2-propanediol di (meth) acrylate, 1, 3-propanediol di (meth) acrylate, 1, 3-butanediol di (meth) acrylate, 1, 4-Butan
  • Di-unsaturated monomers in particular divinylbenzene and 1, 3-butanediol di (meth) acrylate and 1, 4-butanediol di (meth) acrylate, are preferred.
  • conjugated di-or polyunsaturated monomers can also be used.
  • plasticizers are based on azelates, alkylsulfonic acid phenyl esters, azelates, benzoates, chlorinated paraffins, citrates, epoxides, ricinolates, phosphates, valerates, phthalates, sebacates, terephthalates and trimellitates. Plasticizers based on adipic acid, azelaic acid and sebacic acid are particularly preferred.
  • the graft copolymers are prepared by emulsion polymerization.
  • emulsifiers e.g. sodium, potassium or ammonium salts of saturated or unsaturated C8-C20 fatty acids such as lauric acid, stearic acid, palmitic acid, oleic acid and others, C8-C20-alkylsulfonic acids, sulfuric acid-C8-C20-alkyl esters, alkylbenzenesulfonic acids, abiethic acid and their derivatives, sulfosuccinic acid alkyl Diphenyl ether sulfonic acids.
  • C8-C20 fatty acids such as lauric acid, stearic acid, palmitic acid, oleic acid and others
  • C8-C20-alkylsulfonic acids sulfuric acid-C8-C20-alkyl esters
  • alkylbenzenesulfonic acids abiethic acid and their derivatives
  • the particle size of the emulsion can be adjusted in a known manner. It can be between 50 and 300 nm. It is preferably in the range from 70 to 250 nm, particularly preferably between 70 and 200 nm. Both the optical properties (transparency, opalescence) and the mechanical properties (impact strength) are influenced by the particle size.
  • Thermally decomposing initiators or redox systems can be used as initiators.
  • Suitable thermally decomposing initiators are, for example, sodium, potassium or ammonium persulfate and water-soluble azo compounds such as the sodium salt of 4, 4'-azobis (4, 4'-cyanopentanoic acid) .
  • suitable redox systems are cumene hydroperoxide, diisopropylbenzene hydroperoxide, tert-butyl hydroperoxide, tert-butyl peracetate in combination with reducing agents such as sodium formaldehyde sulfoxylate or ascorbic acid in the presence of iron salts.
  • the persulfates mentioned can also be used in combination with reducing agents such as sodium or potassium metabisulfite in redox systems.
  • the polymerization temperature is generally between 10 and 100°C, preferably 50 to 90°C.
  • Example 1 (comparative example based on example 1 in EP 0527605)
  • Step 1 making the core
  • the emulsified monomer mixture is prepared in a beaker with a stirrer from 440 g of water, 10 mL of a dilute solution (25%) of sodium dodecyl sulfate, 1440 g of butyl acrylate and 10 g of allyl methacrylate.
  • the 2nd amount of EMG is then added at 180 g, followed by 0.9 g BHP.
  • the cycle “exothermic reaction-15 min stirring-cooling” is repeated.
  • Step 2 making the shell
  • the end product has:
  • Step 1 making the core
  • the emulsified monomer mixture is prepared in a beaker with a stirrer from 440 g of water, 10 ml of a dilute solution (25%) of sodium dodecyl sulfate, 360 g of di-i-nonyl adipate, 1080 g of butyl acrylate and 10 g of allyl methacrylate.
  • the 2nd amount of EMG is then added at 180 g, followed by 0.9 g BHP.
  • the cycle “exothermic reaction-15 min stirring-cooling” is repeated.
  • Step 2 making the shell
  • the end product has:
  • the present invention provides a graft copolymer with core-shell structure, characterized in that the core is produced by several steps of a successive emulsion polymerization of one or more monomers in the presence of one or more plasticizers, the plasticizer content being 10 to 80%and the monomer content being 90 to 10%.
  • the monomers are selected from the group C1-C12-alkyl acrylates, C1-C12-alkyl methacrylates, styrene and its substituted derivatives as well as vinyl ethers, vinyl esters or vinyl propionate.
  • plasticizers are selected from the group consisting of azelate, phenyl alkylsulfonic acid, azelates, benzoates, chlorinated paraffins, citrates, epoxies, ricinolates, phosphates, valerates, phthalates, sebacates, terephthalates and trimellitates.
  • plasticizers are selected from the group dibutyl adipate, di (2-ethylhexyl) adipate, di-decyl adipate, di-i-nonyl adipate, di-i-octyl adipate, di-i-tridecyl adipate, Di-n-octyl adipate, dibutylazelate, di (2-ethylhexyl) azelate, di-decylazelate, di-i-nonylazelate, di-i-octylazelate, di-i-tridecylazelate, di-n-octylazelate, dibutyl sebazate, di (2-ethylhexyl) sebazate, di-decyl sebazate, di-i-nonyl sebazate, di-i-octyl sebazate, di-i-o
  • the present invention also provides a process for the preparation of the graft copolymers, including:
  • a latex from rubber-like polymer particles with a glass transition temperature Tg ⁇ -20°C and a particle size of 50 to 300 nm in diameter is formed by emulsion polymerization
  • b. are predominantly formed from units derived from methyl methacrylate
  • a. are predominantly formed from units derived from methyl methacrylate
  • the final core-shell polymer is isolated by (a) spray drying or (b) coagulating, preferably by adding an aqueous solution of an inorganic acid salt.
  • the present invention further provides a process for producing a thermoplastic resin comprising:
  • thermoplastic resin optionally processed into an article by extrusion, calendering or injection molding.
  • the thermoplastic resin is a homo-or copolymer of vinyl chloride, a chlorinated PVC or a homo-or copolymer of methyl methacrylate or a technical resin such as a polyester of terephthalic acid and an aliphatic glycol, a polyamide, a polycarbonate B. a polyglutarimide, an acrylonitrile-butadiene-styrene resin or a mixture of at least two such resins.
  • the present invention provides a mixture comprising 60 to 99%by weight of a thermoplastic polymer and 1 to 40%by weight of the core-shell graft copolymer or produced by a process.
  • the mixture further contains one or more constituents: lubricant, processing aid, rheology modifier, dye, pigment, flame retardant, heat stabilizer, antioxidant, antiozonant, ultraviolet stabilizer, mold release agent, reinforcing or non-reinforcing filler.
  • the disclosure provides a graft copolymer with core-shell structure, the core is produced by several steps of a successive emulsion polymerization of one or more monomers in the presence of one or more plasticizers, the plasticizer content is 10 to 80%and the monomer content is 90 to 10%. Ifthe plasticiser content is ⁇ 10%, the graft copolymer shows no or a very minor effect to decrease the glass transition temperature. If the plasticiser content is>80%, the graft copolymer is impossible to graft the shell on the surface of the rubbery core. If the monomer content is>90%, the graft copolymer shows no or a very minor effect to decrease the glass transition temperature.
  • the graft copolymer is impossible to graft the shell on the surface of the rubbery core.
  • the graft copolymer with core-shell structure ensures impact modifiers for low temperature applications with good transparency and weatherability.
  • the particle size of a nonmelting additive in PVC always has an influence on its performance.
  • a particle too small or too large may not induce the optimum impact strength.
  • the 200 nm size seems to comprise the borderlines between various mechanisms that are happening during impact. Meanwhile, at a lower particle size ( ⁇ 200 nm) crazing dominates the energy absorption.
  • the mixture comprises 60 to 99%by weight of a thermoplastic polymer and 1 to 40%by weight of the core-shell graft copolyme.
  • the addition level of impact modifiers influences several parameters. A small increase in Charpy and Izod impacts strengths at low dosages. A rapid increase in Charpy and Izod impacts strengths at slightly higher dosages. Again a small improvement of impact strengths when the amount of modifier is further increased, a decrease in impact strength at high dosages, a decrease in tensile strength with increasing modifier load, an increase in both melt viscosity and cost with increasing amounts of impact modifier.
  • the minimum dosage of modifier should be 1%to see an increase of impact strength and that 40%is the point when impact strength may drop again. According to this the thermoplastic resin must vary in a range from 60 to 99%.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Graft Or Block Polymers (AREA)

Abstract

L'invention concerne un copolymère greffé ayant une structure cœur-enveloppe, un procédé de préparation des copolymères greffés, un procédé de production d'une résine thermoplastique, et un mélange du copolymère greffé avec une structure cœur-enveloppe. Le cœur est produit par plusieurs étapes d'une polymérisation en émulsion successive d'un ou plusieurs monomères en présence d'un ou de plusieurs plastifiants, la teneur en plastifiant étant de 10 à 80 % et la teneur en monomères étant de 90 à 10 %. Le copolymère greffé à structure cœur-enveloppe assure des modificateurs d'impact pour des applications à basse température avec une bonne transparence et une bonne résistance aux intempéries.
PCT/CN2020/093801 2019-06-03 2020-06-01 Modificateurs d'impact à basse température ayant une bonne transparence et une bonne résistance aux intempéries Ceased WO2020244485A1 (fr)

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CN202080041498.XA CN114174386A (zh) 2019-06-03 2020-06-01 具有良好透明度和耐候性的低温抗冲改性剂

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007055550A1 (fr) * 2005-11-14 2007-05-18 Kolon Industries Inc. Perles de polymere acrylique et composition de solution les contenant
WO2015024882A1 (fr) * 2013-08-22 2015-02-26 Basf Se Procédé de production de polymères en émulsion
US20180319918A1 (en) * 2016-01-25 2018-11-08 AGC Inc. Powder coating material, method for producing substrate provided with coating film and coated article
CN110872397A (zh) * 2018-08-31 2020-03-10 富士施乐株式会社 树脂组合物和树脂成型制品

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW241270B (fr) * 1991-08-13 1995-02-21 Rohm & Haas
WO1994004581A1 (fr) * 1992-08-13 1994-03-03 Ppg Industries, Inc. Latex a base aqueuse, adaptes a l'application par pulverisation
WO2016058096A1 (fr) * 2014-10-15 2016-04-21 Terraverdae Bioworks Inc. Films biopolymères bioactifs et revêtements

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007055550A1 (fr) * 2005-11-14 2007-05-18 Kolon Industries Inc. Perles de polymere acrylique et composition de solution les contenant
WO2015024882A1 (fr) * 2013-08-22 2015-02-26 Basf Se Procédé de production de polymères en émulsion
US20180319918A1 (en) * 2016-01-25 2018-11-08 AGC Inc. Powder coating material, method for producing substrate provided with coating film and coated article
CN110872397A (zh) * 2018-08-31 2020-03-10 富士施乐株式会社 树脂组合物和树脂成型制品

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