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CN-121975056-A - Acrylic ester-styrene-acrylonitrile polymer resin containing carboxylic acid side chain, resin composition containing acrylic ester-styrene-acrylonitrile polymer resin and preparation method of resin composition

CN121975056ACN 121975056 ACN121975056 ACN 121975056ACN-121975056-A

Abstract

The invention provides an acrylic ester-styrene-acrylonitrile polymer resin containing carboxylic acid side chains, a resin composition containing the same and a preparation method thereof. The addition of the monomer containing carboxylic vinyl can make the polymer resin stably proceed by suspension polymerization without adding dispersing isolation substance, and the resin product has light transmittance of more than or equal to 90%, haze of less than or equal to 3% and weight average molecular weight of 10-30 ten thousand.

Inventors

  • PAN JIEHUI
  • FENG PEIJIN
  • Zhang Gunpeng
  • YAN WEN

Assignees

  • 浙江万盛股份有限公司

Dates

Publication Date
20260505
Application Date
20260305

Claims (16)

  1. 1. An acrylic acid-styrene-acrylonitrile polymer resin containing carboxylic acid side chains, characterized by comprising 50 to 85 wt% of acrylic acid ester monomer units (A), 10 to 35 wt% of phenyl ethylenically unsaturated monomer units (B), 3 to 15 wt% of nitrile ethylenically unsaturated monomer units (C), and 0.01 to 1 wt% of ethylenically unsaturated monomer units (D) containing carboxyl groups, based on the total weight of the acrylic acid-side chains-containing acrylic acid-styrene-acrylonitrile polymer resin.
  2. 2. The acrylic acid group side chain-containing acrylic acid ester-styrene-acrylonitrile polymer resin according to claim 1, wherein 60 to 80 wt% of the acrylic acid ester monomer unit (A), 15 to 30 to wt% of the phenyl vinyl unsaturated monomer unit (B), 4 to 12 to wt% of the nitrile vinyl unsaturated monomer unit (C), and 0.05 to 0.5 to wt% of the carboxyl group-containing vinyl unsaturated monomer unit (D) are contained based on the total weight of the acrylic acid group side chain-containing acrylic acid ester-styrene-acrylonitrile polymer resin.
  3. 3. The acrylic acid ester-styrene-acrylonitrile polymer resin containing a side chain of a carboxylic acid group according to claim 1, wherein said ethylenically unsaturated monomer unit (D) containing a carboxylic acid group has a general structural formula of CH 2 =CR 5 -COOR 6 ; Wherein R 5 is H or C 1-6 alkyl, R 6 is H, na, K, a polyethylene glycol chain or a hydrophilic group of a polyvinyl alcohol chain, preferably R 5 is H or C 1-3 alkyl, R 6 is H, na, or K, more preferably R 5 is H or methyl, and R 6 is H.
  4. 4. The acrylic acid ester-styrene-acrylonitrile polymer resin containing carboxylic acid group side chains according to claim 1, wherein said acrylic acid ester monomer unit (A) has a general structural formula of CH 2 =CR 1 -COOR 2 ; Wherein R 1 is H or C 1-3 alkyl, R 2 is C 1-4 straight or branched alkyl, C 3-10 cycloalkyl or aryl, preferably R 1 is H or methyl, and R 2 is C 1-4 alkyl or phenyl.
  5. 5. The acrylic acid ester-styrene-acrylonitrile polymer resin containing carboxylic acid group side chains according to claim 1, wherein said phenylethylenically unsaturated monomer unit (B) has a general structural formula of CH 2 =CR 3 -C 6 H 5 ; Wherein R 3 is H or C 1-3 alkyl, preferably R 3 is H or methyl.
  6. 6. The acrylic acid ester-styrene-acrylonitrile polymer resin containing carboxylic acid group side chains according to claim 1, wherein said nitrile group ethylenically unsaturated monomer unit (C) has a general structural formula of CH 2 =CR 4 -CN; Wherein R 4 is H or C 1-3 alkyl, preferably R 4 is H or methyl.
  7. 7. The acrylic acid ester-styrene-acrylonitrile polymer resin having a side chain of a carboxylic acid group according to claim 1 to 6, wherein said resin is a spherical transparent solid having an average particle diameter of 0.2 to 2 mm.
  8. 8. The acrylic acid ester-styrene-acrylonitrile polymer resin having side chains of carboxylic acid groups according to claim 1 to 6, wherein said resin has an acid value of 0.3 to 2.5 mg KOH/g.
  9. 9. The acrylic acid ester-styrene-acrylonitrile polymer resin having side chains of carboxylic acid groups according to claim 1 to 6, wherein the weight average molecular weight of the resin is 10 to 30 ten thousand, the melt index is 10 to 45 g/10min, and the glass transition temperature is 90 to 110 ℃.
  10. 10. The acrylic acid ester-styrene-acrylonitrile polymer resin according to claim 1 to 6, wherein said resin has a light transmittance of 90% or more, a haze of 3% or less, and a refractive index of 1.5100 to 1.5300.
  11. 11. A process for the preparation of an acrylate-styrene-acrylonitrile polymer resin containing carboxylic acid side chains according to any one of claims 1 to 10, characterized by comprising the steps of: (1) Suspension polymerization is carried out on an acrylic acid ester monomer unit (A), a phenyl alkene unsaturated monomer unit (B), a nitrile alkene unsaturated monomer unit (C) and a carboxyl group-containing alkene unsaturated monomer unit (D) to obtain a suspension; (2) Filtering, washing and drying the suspension to obtain the acrylic ester-styrene-acrylonitrile polymer resin containing carboxylic acid side chains.
  12. 12. The method of claim 11, wherein no dispersion barrier substance is added during the suspension polymerization in step (1).
  13. 13. The process according to claim 11 or 12, wherein the solids content of the suspension in step (1) is 15-35%.
  14. 14. A resin composition characterized in that: An impact modifier comprising the acrylic-styrene-acrylonitrile polymer resin having a carboxylic acid group side chain as defined in any one of claims 1 to 10 and a core-shell structure.
  15. 15. The resin composition of claim 14, wherein: The impact modifier of the core-shell structure is selected from one or more of methyl methacrylate-acrylonitrile-butadiene-styrene graft copolymer, methyl methacrylate-butadiene-styrene graft copolymer, and acrylonitrile-butadiene-styrene graft copolymer, preferably methyl methacrylate-acrylonitrile-butadiene-styrene graft copolymer.
  16. 16. The resin composition according to claim 14 or 15, wherein: The content of the acrylic acid ester-styrene-acrylonitrile polymer resin containing carboxylic acid group side chains is 40 to 90 wt%, preferably 45 to 85 wt%, more preferably 50 to 80 wt%, relative to 100 wt% of the resin composition.

Description

Acrylic ester-styrene-acrylonitrile polymer resin containing carboxylic acid side chain, resin composition containing acrylic ester-styrene-acrylonitrile polymer resin and preparation method of resin composition Technical Field The invention belongs to the field of high polymer materials, and particularly relates to an acrylic ester-styrene-acrylonitrile polymer (MSAN) resin containing carboxylic acid side chains, a resin composition containing the MSAN resin, and a preparation method of the MSAN resin. Background In the traditional transparent materials, styrene-acrylonitrile copolymer (SAN for short), polystyrene (PS for short) and polymethyl methacrylate (PMMA for short) resins have poor impact performance, and polycarbonate (PC for short) resins have low chemical resistance and high price, and high impact polystyrene (HIPS for short) has low chemical resistance and is easy to scratch, so that the application range of the styrene-acrylonitrile copolymer (SAN for short), polystyrene for short and polymethyl methacrylate (PMMA for short) resins is limited. In recent years, a methyl methacrylate-styrene-acrylonitrile copolymer (abbreviated as MSAN) has been developed as a transparent resin which can be processed and molded, and a thermoplastic resin composition, which is generally called a transparent ABS resin having excellent mechanical properties, processability and optical properties, is formed by adding an impact modifier having a core-shell structure such as a methyl methacrylate-acrylonitrile-butadiene-styrene graft copolymer (abbreviated as MABS), and is generally used for manufacturing transparent parts such as a cover plate of a washing machine, a housing of a monitor and a housing of a game machine, which are suitable for processing processes such as injection molding, extrusion, calendaring and blow molding. Currently, MSAN is mainly prepared by suspension polymerization, i.e., a method in which raw monomers such as methyl methacrylate, styrene and acrylonitrile are dissolved in an organic phase, and then the organic phase is added to an aqueous phase and suspended in water to perform polymerization (so-called suspension polymerization), and it is required to ensure that the monomer-containing organic phase is dispersed in the aqueous phase in the form of droplets, each of which is a reaction unit. Therefore, if the liquid drops are too large, the heat exchange effect is poor, the molecular weight distribution of the obtained polymer is widened and even the system is unstable due to the too high local temperature of the reaction unit, and the polymer is agglomerated and agglomerated due to the instability of the system, and if the liquid drops are too small, emulsion polymerization reaction is easy to occur, so that the product cannot be obtained through a normal post-treatment process. In order to allow the monomer-containing organic phase to be distributed in the aqueous phase in droplets of a suitable size during suspension polymerization, it is generally necessary to add an oligomer containing anions or cations, fine powders of polyvinyl alcohol or inorganic salts (such as calcium carbonate) or the like as dispersion-isolating substances, but these dispersion-isolating substances tend to remain in the polymer product easily and to be difficult to clean, and these remaining dispersion-isolating substances significantly reduce the light transmittance, haze and mechanical properties of the polymer product. Disclosure of Invention Problems to be solved by the invention At present, the performances such as light transmittance and haze of the product can be influenced by the separation isolation substance added in the process of preparing the transparent resin product, and improvement of the transparency (mainly comprising the light transmittance and the haze) of the product is urgent. In view of the above facts, the present invention has an object to provide an acrylate-styrene-acrylonitrile polymer resin (MSAN) having remarkably improved transparency, and to provide a method for producing the MSAN resin by introducing a monomer containing a carboxylic acid group vinyl group using a suspension polymerization method without adding a dispersion barrier substance, the reaction being stabilized and the process not occurring agglomerated, and a resin composition containing the MSAN resin. Means for solving the problems Through a series of researches, the inventor takes acrylate monomer units, phenyl alkene unsaturated monomer units, nitrile alkene unsaturated monomer units and alkene unsaturated monomer units containing carboxyl as raw materials, and polymerizes all the monomer units to form acrylate-styrene-acrylonitrile polymer resin (MSAN resin for short) containing carboxylic acid side chains on the premise of not introducing dispersion isolation substances, wherein the MSAN resin is uniformly transparent pellets with the average diameter of 0.2-2mm, the light transmittance is more than or equal t