CN110372817B - Preparation method of nano metal oxide modified thermal expansion microspheres - Google Patents

Preparation method of nano metal oxide modified thermal expansion microspheres Download PDF

Info

Publication number
CN110372817B
CN110372817B CN201910712346.7A CN201910712346A CN110372817B CN 110372817 B CN110372817 B CN 110372817B CN 201910712346 A CN201910712346 A CN 201910712346A CN 110372817 B CN110372817 B CN 110372817B
Authority
CN
China
Prior art keywords
weight
parts
metal oxide
thermal expansion
oxide modified
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.)
Active
Application number
CN201910712346.7A
Other languages
Chinese (zh)
Other versions
CN110372817A (en
Inventor
呼建强
姜丽娜
马超
刘翰卿
张振东
吴凯
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.)
Shandong Yuanbang New Material Co ltd
Original Assignee
Shandong Yuanbang New Material Co ltd
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 Shandong Yuanbang New Material Co ltd filed Critical Shandong Yuanbang New Material Co ltd
Priority to CN201910712346.7A priority Critical patent/CN110372817B/en
Publication of CN110372817A publication Critical patent/CN110372817A/en
Application granted granted Critical
Publication of CN110372817B publication Critical patent/CN110372817B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/18—Suspension polymerisation
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00—Characterised by the use 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 an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene
    • C08J2325/06—Polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use 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; Derivatives of such polymers
    • C08J2327/02—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/04—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08J2327/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2265—Oxides; Hydroxides of metals of iron
    • C08K2003/2272—Ferric oxide (Fe2O3)
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing Of Micro-Capsules (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

The invention relates to a preparation method of a microsphere foaming agent, in particular to a preparation method of nanometer metal oxide modified thermal expansion microspheres. Water phase composed of saturated saline, emulsifier, wetting agent, emulsifying dispersant, pH regulator, functional water-soluble monomer, nano metal oxide, etc.; an oil phase consisting of a propylene mixed monomer, a low boiling point liquid, a cross-linking agent, an antioxidant, a functional oil-soluble monomer, a redox initiation system and the like; the inorganic-organic polymer composite expanded microspheres are prepared by adopting a one-time feeding and ultralow temperature suspension polymerization process, and the surface of the shell polymer material is modified by metal oxide, so that the heat conduction performance, the high-temperature heat resistance and the shell polymer layer rigidity are improved while the original basic performances such as expansion multiple, particle size and particle size distribution are maintained. The application field of the thermal expansion microspheres is widened, and the method is suitable for more severe processing conditions.

Description

Preparation method of nano metal oxide modified thermal expansion microspheres
Technical Field
The invention relates to a preparation method of a microsphere foaming agent, in particular to a preparation method of nanometer metal oxide modified thermal expansion microspheres.
Background
The high molecular foaming material is prepared by adding auxiliary materials such as a bubble stabilizer (foam stabilizer), a chemical foaming agent, a physical foaming agent and the like into raw materials such as a base material, a plasticizer, a heat stabilizer, a processing aid, a foaming regulator and the like, and extruding, injecting, molding or die pressing the raw materials to enable a large number of fine bubbles to appear in plastic, so that the volume is increased and the density is reduced. For example, the soft PVC foam material has light weight and good softness, has the functions of buffering, sound absorption, shock absorption, heat preservation, filtration and the like, and is widely applied to the industries of advertisement, electronics, household appliances, automobiles, sports and leisure, decorative materials, yachts, aerospace, building energy conservation and the like.
In recent years, China realizes multiple innovations in the formula design and production process of chemical foaming agents and physical foaming agents, the product performance is gradually improved, the application field is gradually widened, and the innovations can further promote the polymer foaming material industry to realize faster development.
At present, the synthesis method of the thermal expansion microsphere has more domestic and foreign patents and literature reports, and the thermal expansion microsphere is mainly prepared by taking a low-boiling alkane foaming agent as a nuclear layer component and taking acrylonitrile and/or acrylate monomers as a shell layer component through a suspension polymerization method. The foaming capacity and processing form of the thermally expandable microspheres are influenced by a plurality of factors such as the composition of the foaming agent, the composition of the shell wall polymer, the ratio of the foaming agent to the shell wall polymer, the size and distribution of the microspheres and the like, so that the regulation and control of the foaming performance of the microspheres are complex.
Through searching relevant patents and documents at home and abroad, the research results of synthesis and application of magnetic polymer materials are infinite, and become one of the hotspots in the research field of functional polymer materials at present. At present, many researches are conducted at home and abroad on magnetic high polymer materials, but the method still falls into the blank in the field of nano metal oxide modified thermal expansion microspheres.
Disclosure of Invention
The invention aims to provide a preparation method of nano metal oxide modified thermal expansion microspheres, which comprises the following steps of preparing a water phase consisting of saturated saline water, an emulsifier, a wetting agent, an emulsifying dispersant, a pH regulator, a functional water-soluble monomer, nano metal oxide and the like; an oil phase consisting of a propylene mixed monomer, a low boiling point liquid, a cross-linking agent, an antioxidant, a functional oil-soluble monomer, a redox initiation system and the like; the magnetic thermal expansion microspheres are prepared by adopting a one-time feeding and ultralow temperature suspension polymerization process.
The surface of the shell layer high molecular material is modified by the metal oxide, so that the heat conduction performance, the high-temperature heat resistance and the shell layer high molecular layer rigidity are improved while the original basic performances such as expansion multiple, particle size and particle size distribution are maintained, the application field of the thermal expansion microsphere is widened, and the harsh processing conditions are adapted.
The preparation method of the nanometer metal oxide modified thermal expansion microsphere comprises the following steps:
(1) adding 80-100 parts by weight of saturated saline, 0.5-3.0 parts by weight of emulsifier, 0.01-0.05 part by weight of wetting agent, 5-20 parts by weight of emulsifying dispersant, 0.002-2.0 parts by weight of pH regulator, 1-5 parts by weight of functional water-soluble monomer and 0.001-0.2 part by weight of nano metal oxide powder into a pressure reaction kettle, discharging oxygen by using nitrogen, starting stirring, controlling the rotating speed to be 50-1000r/min, heating to 35-40 ℃, and stirring for 10-30 min to form a water phase;
(2) uniformly mixing 80-100 parts by weight of propylene mixed monomer, 20-50 parts by weight of low boiling point liquid, 1-5 parts by weight of cross-linking agent, 0.2-0.8 part by weight of antioxidant, 1-5 parts by weight of functional oil-soluble monomer and 0.05-2.0 parts by weight of redox initiator to form an oil phase;
(3) mixing the oil phase and the water phase according to the weight ratio of 1-4.5: 5, mixing, heating to 38-55 ℃ under the conditions of 50-2000r/min, 0.5-1.5MPa of rotation speed and stirring, controlling the reaction temperature at 38-55 ℃, reacting for 3-24h, heating to 50-55 ℃, curing for 1-2h, then cooling to 20-30 ℃, discharging, filtering and drying to obtain a product;
wherein:
the propylene mixed monomer comprises the following monomers in percentage by weight:
1-5% of functional monomer, 5-35% of acrylonitrile, 0-20% of acrylic acid and 60-94% of methacrylic acid;
the functional monomer is alkyl methacrylate or alkyl acrylate monomer;
the nano metal oxide is one or more of nano iron oxide, nano aluminum oxide and nano zinc oxide.
The particle size of the polymer microsphere foaming agent is 5.5-55 mu m.
Preferably, the functional monomer is one or two of 2-hydroxyethyl methacrylate, glycidyl methacrylate or isobornyl methacrylate, and the dosage is preferably 2-3%.
The saturated saline is one or a mixture of magnesium sulfate and sodium chloride, and the using amount of the saturated saline is preferably 80-95 parts.
The emulsifier is one or a mixture of NP-10 (nonylphenol polyoxyethylene ether 10), OP-10 or Tween-80, and the dosage of the emulsifier is preferably 2.0 to 2.5 parts; the wetting agent is one or a mixture of diisobutyl naphthalene sulfonate, dialkyl succinate sodium sulfonate, 2-ethylhexanol polyoxyethylene ether phosphate, methylene dinaphthalene sodium sulfonate or dodecyl alcohol polyoxyethylene ether, and the dosage of the wetting agent is preferably 0.02-0.03 parts; the emulsifying dispersant is one or a mixture of polyvinyl alcohol, sodium pyrophosphate, nano silicon dioxide, polyvinylpyrrolidone, trisodium phosphate, sodium dihydrogen phosphate or hydrotalcite, and the using amount of the emulsifying dispersant is preferably 10-15 parts.
The nano silicon dioxide is preferably prepared into colloidal silicon dioxide for use.
The pH regulator is one or more of hydrochloric acid, succinic acid, adipic acid, citric acid, salicylic acid or tartaric acid used in a mixture of 20-25 wt.%, and the use amount is preferably 0.005-2.0 parts, and the pH of the reaction system is controlled to be 1-6.
The functional water-soluble monomer is one or a mixture of more of methacrylamide, dimethylacrylamide, dimethylaminoethyl acrylate, dimethyl diallyl ammonium chloride or methacryloyloxyethyl trimethyl ammonium chloride, and the dosage of the functional water-soluble monomer is preferably 2-3 parts; the functional oil-soluble monomer is one or a mixture of N-phenyl maleimide, N-dimethylacrylamide, vinyl trichlorosilane or gamma-chloropropyl trichlorosilane, and the dosage of the functional oil-soluble monomer is preferably 2-5 parts.
The low-boiling-point liquid is one or a mixture of more of n-butane, isobutane, isooctane, isopentane or petroleum ether, and the using amount of the low-boiling-point liquid is preferably 20-40 parts.
The cross-linking agent is one or a mixture of dipentaerythritol hexaacrylate, hexanediol diacrylate, dimethylaminoethyl acrylate, ethylene glycol dimethacrylate, butanediol dimethacrylate or trimethylolpropane triacrylate (TMPTA), and the using amount of the cross-linking agent is preferably 2-3 parts.
The redox initiator consists of an oxidizing agent and/or a reducing agent; preferably an oxidizing agent and a reducing agent, wherein the oxidizing agent accounts for 20-80%, preferably 50-70% of the total mass of the redox initiator, and the balance is the reducing agent; the oxidant is one or more of persulfate, peroxyacid salt or alkali metal peroxide; the reducing agent is one or more of sulfurous acid and salts thereof, bisulfite, thiosulfate, formaldehyde sulfoxylate, pyrosulfite alkali metal salts or pyrobisulfite.
Preferably, the oxidant is one or more of potassium persulfate, ammonium persulfate, dibenzoyl peroxide, dicumyl peroxide, tert-butyl peroxybenzoate and di-tert-butyl peroxide; the reducing agent is one or more of sodium bisulfite, sodium dithionite, sodium formaldehyde sulfoxylate or sodium metabisulfite.
Preferably, in the step (3), the weight ratio of the oil phase to the water phase is 2.5-4.0: 5, the reaction pressure is 0.6-1.0MPa, and the reaction temperature is 38-50 ℃.
The antioxidant is an antioxidant 1076.
In the invention, after the reaction is started, the reaction temperature is controlled by circulating water in a jacket of the reaction kettle.
The nano oxide modified thermal expansion microspheres prepared by the invention can be widely applied to functional plastic foaming products (PS, TPU and the like); PVC foamed articles such as: foaming soles, plasticine, handrails, wallpaper and other fields; the low-calcium filling extrusion product such as foaming section bars, profile bars, foaming plates, foaming pipes, foaming plates, building templates, Wood Plastic (WPC), wall plates and other products partially or completely replaces the traditional chemical foaming agent and physical foaming agent, and has wide market prospect.
In conclusion, the beneficial effects of the invention are as follows:
(1) according to the invention, through the coordination of the emulsifier, the wetting agent, the emulsifying dispersant and different stirring speeds, the suspension polymerization process is adopted, the solid content of the prepared polymer microsphere suspension is high, and the single-kettle yield is improved by 10%.
(2) The preparation method is simple to operate, stable and stable in heat release, capable of recycling saturated brine, capable of reducing comprehensive consumption of products per ton by 20% and stable in product quality, and suitable for industrial mass production.
(3) The surface of the modified microsphere shell layer contains functional polar groups such as hydroxyl, amido, carboxyl and the like, and the functional rigid monomer and the flexible monomer are highly crosslinked and copolymerized, so that the viscoelasticity is moderate. The PVC shell material has stronger cohesiveness with PVC and other material base materials, the probability of the wall breaking phenomenon is greatly reduced in the extrusion molding process and the using process of the low-calcium filled PVC product, and the negative influence of high shear pressure on the shell hardness brought in the extrusion process is reduced.
(4) The invention realizes the perfect combination of the inorganic nano metal material and the organic polymer material, and the inorganic nano metal material is uniformly dispersed in the low boiling point liquid of the nuclear layer and the surface and the inner part of the shell layer. The heat resistance, the plasticizing time and the strength of the microspheres are greatly improved, and the application field of the foamed product is wider.
(5) The foaming regulator can partially replace the traditional chemical foaming agent or physical foaming agent, solves the problem of odor residue caused by the decomposition of the traditional chemical foaming agent in the extrusion process of plastic foaming products, particularly PVC foaming products, and effectively reduces the using amount of the foaming regulator.
(6) The nanometer metal oxide modified thermal expansion microspheres have more excellent foaming speed and wider foam stabilizing temperature range, and the bonding performance between the microspheres or between the microspheres and the base material is excellent. Meanwhile, the mechanical strength and the integrity of the wall layer are greatly improved under the action of high temperature and high shear. The application of the thermal expansion microspheres in functional plastic foaming products (PVC, PS, TPU and the like) is widened.
Drawings
FIG. 1 is a schematic view showing the nano metal oxide-modified heat-expandable microspheres of the present invention.
Detailed Description
The present invention will be further described with reference to the following examples.
All the starting materials used in the examples are commercially available, except where otherwise indicated.
Example 1
The preparation method of the nanometer metal oxide modified thermal expansion microsphere comprises the following steps:
(1) adding 100 parts by weight of saturated saline (magnesium sulfate/sodium chloride is 5/5), 0.5 part by weight of emulsifier NP-10, 0.03 part by weight of wetting agent diisobutylnaphthalenesulfonate, 20 parts by weight of emulsifying dispersant nano-silica, 0.01 part by weight of pH regulator 20 wt.% hydrochloric acid, 5 parts by weight of functional water-soluble monomer methacrylamide and 0.001 part by weight of nano-metal oxide nano-iron oxide into a pressure reaction kettle, discharging oxygen by nitrogen, starting stirring, controlling the rotation speed to 1000r/min, heating to 35 ℃, and stirring for 30min to form a water phase;
(2) uniformly mixing 100 parts by weight of acrylic mixed monomers (1% of 2-hydroxyethyl methacrylate, 35% of acrylonitrile, 16% of acrylic acid and 48% of methacrylic acid), 20 parts by weight of low boiling point liquid (18 parts of isopentane and 2 parts of petroleum ether), 3 parts by weight of cross-linking agent trimethylolpropane triacrylate (TMPTA), 0.2 part by weight of antioxidant beta- (3,5 di-tert-butyl-4-hydroxyphenyl) N-octadecyl propionate (1076), 3 parts by weight of functional oil-soluble monomer N-phenyl maleimide and 2.0 part by weight of initiator di (2-ethylhexyl) peroxydicarbonate to form an oil phase;
(3) mixing the oil phase and the water phase according to the ratio of 1: mixing at a ratio of 5 (weight ratio), heating to 38 deg.C under stirring at a rotation speed of 0.5MPa at 500r/min, controlling the reaction temperature at 38 + -1 deg.C, reacting for 24h, heating to 50 deg.C, aging for 2h, cooling to 20 deg.C, discharging, filtering, washing with water, and drying to obtain the final product.
Example 2
The preparation method of the nanometer metal oxide modified thermal expansion microsphere comprises the following steps:
(1) adding 100 parts by weight of saturated sodium chloride brine, 2.5 parts by weight of emulsifier OP-10, 0.05 part by weight of wetting agent sodium methylene dinaphthalene sulfonate, 5 parts by weight of emulsifying dispersant hydrotalcite, 0.005 part by weight of pH regulator citric acid, 2 parts by weight of functional water-soluble monomer dimethylaminoethyl acrylate and 0.2 part by weight of nano metal oxide nano aluminum oxide into a pressure reaction kettle, discharging oxygen by using nitrogen, starting stirring, controlling the rotating speed to be 1000r/min, heating to 38 ℃, and stirring for 30min to form a water phase;
(2) uniformly mixing 100 parts by weight of acrylic acid mixed monomer (2% of glycidyl methacrylate, 30% of acrylonitrile and 68% of methacrylic acid), 40 parts by weight of low boiling point liquid (18 parts of isooctane and 22 parts of isopentane), 2 parts by weight of cross-linking agent butanediol dimethacrylate, 0.2 part by weight of antioxidant beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) N-octadecyl propionate (1076), 5 parts by weight of functional oil-soluble monomer N, N-dimethylacrylamide and 2.0 part by weight of redox initiator tert-butyl peroxybenzoate to form an oil phase;
(3) mixing the oil phase and the water phase according to the ratio of 2: mixing at a ratio of 5 (weight ratio), heating to 40 deg.C under stirring at a rotation speed of 0.65MPa at 1000r/min, controlling the reaction temperature at 44 + -1 deg.C, reacting for 20h, heating to 50 deg.C, aging for 2h, cooling to 20 deg.C, discharging, filtering, washing with water, and drying to obtain the final product.
Example 3
The preparation method of the nanometer metal oxide modified thermal expansion microsphere comprises the following steps:
(1) adding 100 parts by weight of saturated magnesium sulfate saline, 2.0 parts by weight of emulsifier Tween-80, 0.05 part by weight of wetting agent dodecyl alcohol polyoxyethylene ether, 15 parts by weight of emulsifying dispersant nano silicon dioxide, 2.0 parts by weight of pH regulator salicylic acid, 3 parts by weight of functional water-soluble monomer methacrylamide and 0.05 part by weight of nano metal oxide nano zinc oxide into a pressure reaction kettle, discharging oxygen by using nitrogen, starting stirring, controlling the rotating speed to be 800r/min, heating to 40 ℃, and stirring for 30min to form a water phase;
(2) uniformly mixing 100 parts by weight of acrylic acid mixed monomers (1% of dimethylaminoethyl acrylate, 30% of acrylonitrile and 69% of methacrylic acid), 30 parts by weight of low-boiling-point liquid (5 parts of isobutane, 20 parts of isooctane and 5 parts of petroleum ether), 3 parts by weight of cross-linking agent ethylene glycol dimethacrylate, 0.6 part by weight of antioxidant beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate (1076), 5 parts by weight of functional oil-soluble monomer gamma-chloropropyltrichlorosilane, and 2.0 parts by weight of redox initiator (1.0 part of potassium persulfate and 1.0 part of sodium bisulfite) to form an oil phase;
(3) mixing the oil phase and the water phase according to the ratio of 3: mixing at a ratio of 5 (weight ratio), heating to 50 deg.C under stirring at a rotation speed of 0.65MPa at 800r/min, controlling the reaction temperature at 50 + -1 deg.C, reacting for 12h, heating to 55 deg.C, aging for 2h, cooling to 25 deg.C, discharging, filtering, washing with water, and drying to obtain the final product.
Example 4
The preparation method of the nanometer metal oxide modified thermal expansion microsphere comprises the following steps:
(1) adding 100 parts by weight of saturated sodium chloride saline, 2.0 parts by weight of emulsifier (Tween-80 and NP-10 are respectively 1.0 part and 1.0 part), 0.02 part by weight of wetting agent sodium methylene dinaphthalene sulfonate, 5 parts by weight of emulsifying dispersant colloidal silicon dioxide, 2.0 parts by weight of pH regulator tartaric acid, 1.0 part by weight of functional water-soluble monomer methacryloyloxyethyl trimethyl ammonium chloride and 0.05 part by weight of nano metal oxide nano aluminum oxide into a pressure reaction kettle, discharging oxygen by nitrogen, starting stirring, controlling the rotating speed to 800r/min, heating to 38 ℃, and stirring for 30min to form a water phase;
(2) 100 parts by weight of acrylic acid mixed monomer (1.5 percent of 2-hydroxyethyl methacrylate, 35 percent of acrylonitrile, 11.5 percent of acrylic acid and 52 percent of methacrylic acid), 45.5 parts by weight of low boiling point liquid (5.5 parts of N-butane, 20 parts of isooctane and 20 parts of petroleum ether), 4.5 parts by weight of cross-linking agent dipentaerythritol hexaacrylate, 0.6 part by weight of antioxidant beta- (3,5 di-tert-butyl-4-hydroxyphenyl) propionic acid N-octadecyl ester (1076), 1.50 parts by weight of functional oil-soluble monomer N, N-dimethylacrylamide, 2.0 parts by weight of redox initiator (1.5 parts of tert-butyl peroxybenzoate and 0.5 part of sodium hydrosulfite) are mixed uniformly to form an oil phase;
(3) mixing the oil phase and the water phase according to the weight ratio of 3.5: mixing at a ratio of 5 (weight ratio), heating to 43 ℃ under the conditions of 950r/min, 0.50MPa of rotation speed and stirring, controlling the reaction temperature at 43 +/-1 ℃, reacting for 19 hours, heating to 55 ℃, curing for 1 hour, then cooling to 25 ℃, discharging, filtering, washing with water and drying to obtain the product.
Example 5
The preparation method of the nanometer metal oxide modified thermal expansion microsphere comprises the following steps:
(1) adding 100 parts by weight of saturated sodium chloride saline, 2.0 parts by weight of emulsifier (Tween-80 and OP-10 are respectively 1.8 parts and 0.2 part), 0.04 part by weight of wetting agent sodium methylene dinaphthalene sulfonate, 8 parts by weight of emulsifying dispersant colloidal silicon dioxide, 2.0 parts by weight of pH regulator adipic acid, 3.0 parts by weight of functional water-soluble monomer methacrylamide and 0.05 part by weight of nano metal oxide nano aluminum oxide into a pressure reaction kettle, discharging oxygen by nitrogen, starting stirring, controlling the rotating speed to 850r/min, heating to 38 ℃, and stirring for 30min to form a water phase;
(2) uniformly mixing 100 parts by weight of acrylic acid mixed monomers (2.5% of glycidyl methacrylate, 30% of acrylonitrile, 11.5% of acrylic acid and 56% of methacrylic acid), 38 parts by weight of low boiling point liquid (35.5 parts of isooctane and 2.5 parts of petroleum ether), 1.5 parts by weight of cross-linking agent dipentaerythritol hexaacrylate, 0.6 part by weight of antioxidant beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) N-octadecyl propionate (1076), 1.5 parts by weight of functional oil-soluble monomer N, N-dimethylacrylamide and 0.1 part by weight of redox initiator (0.05 part of tert-butyl peroxybenzoate and 0.05 part of sodium hydrosulfite) to form an oil phase;
(3) mixing the oil phase and the water phase according to the ratio of 2.5: mixing at a ratio of 5 (weight ratio), heating to 45 deg.C under stirring at a rotation speed of 0.50MPa at 950r/min, controlling the reaction temperature at 45 + -1 deg.C, reacting for 20h, heating to 55 deg.C, aging for 1.5h, cooling to 25 deg.C, discharging, filtering, washing with water, and drying to obtain the final product.
Comparative example 1
The preparation method of the embodiment 1 is completely the same as the embodiment 1 except that the nano metal oxide nano iron oxide is removed.
First, basic performance test data comparison
The indexes of the nano metal oxide modified thermal expansion microspheres prepared in examples 1 to 5 and comparative example 1 are shown in table 1.
TABLE 1 Performance index Table
Numbering Average particle diameter (μm) Ts(℃) Inflation height (mL) Retraction time (min)
Comparative example 1 48.9 95 19.8 15
Example 1 49.6 90 19.9 39
Example 2 15.3 135 18.5 60
Example 3 21.8 140 19.6 2h does not retract
Example 4 29.3 150 19.5 2h does not retract
Example 5 18.2 155 19.8 2h does not retract
Note: inflation height and retraction time test conditions: oven 185 ℃ 20mL test tube 0.3g sample 5g weight. Ts is the initial foaming temperature.
Second, comparison of extrusion Process data
0.6 part of each of the nano metal oxide modified thermal expansion microspheres prepared in examples 1 to 5 and 0.6 part of each of the nano metal oxide modified thermal expansion microspheres prepared in comparative example 1 were added
Adding 100 parts of PVC blend, and extruding with a single screw extruder to obtain PVC micro-foaming strips 5mm to 30mm
The properties of (A) are shown in Table 2.
TABLE 2 comparative data of strip density and cross-sectional cell mass
Numbering Density (g/cm)3) Tortuosity (mm/m) Surface hardness (A)
Blank sample 0.55 1.556 55
Comparative example 1 0.50 1.584 55
Example 1 0.46 1.593 54
Example 2 0.48 1.596 55
Example 3 0.45 1.584 53
Example 4 0.45 1.589 53
Example 5 0.46 1.582 55
The formula of the PVC blend is as follows:
100 parts of PVC (SG-8), 4.7 parts of calcium-zinc stabilizer, 10 parts of foaming regulator, 0.5 part of stearic acid, 0.26 part of oxidized polyethylene wax, 5 parts of titanium dioxide, 20 parts of calcium carbonate, 0.6 part of PE wax, 0.35 part of AC foaming agent, 0.7 part of NC foaming agent, 0.015 part of whitening agent, 0.003 part of ultramarine and 15 parts of recycled material.
Third, the comparative examples and comparative examples are compared and analyzed with the plasticizing performance and strength detection data
Respectively adding 6 parts of the nano metal oxide modified thermal expansion microspheres prepared in examples 1-5 and 6 parts of the nano metal oxide modified thermal expansion microspheres prepared in comparative example 1 into the mixture
The results of the tests on 100 parts of PVC blend are shown in Table 3.
Table 3 rheological Property comparison data
Numbering Plastification time(s) Highest torque (Nm) Equilibrium torque (Nm)
Blank sample 192 20.1 19.8
Comparative example 1 185 21.0 20.5
Example 1 165 23.5 22.6
Example 2 162 23.8 23.0
Example 3 164 23.5 22.9
Example 4 160 24.2 23.6
Example 5 166 23.7 22.4
Note: detection conditions of the torque rheometer are as follows: 165 ℃ 15min 35 r/min.
The formula of the PVC blend is as follows:
100 parts of PVC (SG-8), 4.7 parts of calcium-zinc stabilizer, 10 parts of foaming regulator, 0.5 part of stearic acid, 0.26 part of oxidized polyethylene wax, 5 parts of titanium dioxide, 60 parts of calcium carbonate, 0.6 part of PE wax, 0.015 part of whitening agent and 0.003 part of ultramarine.

Claims (9)

1. A preparation method of nanometer metal oxide modified thermal expansion microspheres is characterized by comprising the following steps:
(1) adding 80-100 parts by weight of saturated saline, 0.5-3.0 parts by weight of emulsifier, 0.01-0.05 part by weight of wetting agent, 5-20 parts by weight of emulsifying dispersant, 0.002-2.0 parts by weight of pH regulator, 1-5 parts by weight of functional water-soluble monomer and 0.001-0.2 part by weight of nano metal oxide powder into a pressure reaction kettle, discharging oxygen by using nitrogen, starting stirring, controlling the rotating speed to be 50-1000r/min, heating to 35-40 ℃, and stirring for 10-30 min to form a water phase;
(2) uniformly mixing 80-100 parts by weight of propylene mixed monomer, 20-50 parts by weight of low boiling point liquid, 1-5 parts by weight of cross-linking agent, 0.2-0.8 part by weight of antioxidant, 1-5 parts by weight of functional oil-soluble monomer and 0.05-2.0 parts by weight of redox initiator to form an oil phase;
(3) mixing the oil phase and the water phase according to the weight ratio of 1-4.5: 5, mixing, heating to 38-55 ℃ under the conditions of 50-2000r/min, 0.5-1.5MPa of rotation speed and stirring, controlling the reaction temperature at 38-55 ℃, reacting for 3-24h, heating to 50-55 ℃, curing for 1-2h, then cooling to 20-30 ℃, discharging, filtering and drying to obtain a product;
wherein:
the propylene mixed monomer comprises the following monomers in percentage by weight:
1-5% of functional monomer, 5-35% of acrylonitrile, 0-20% of acrylic acid and 45-70% of methacrylic acid;
the functional monomer is one or two of methacrylic acid-2-hydroxyethyl ester, glycidyl methacrylate or isobornyl methacrylate;
the nano metal oxide is one or more of nano iron oxide, nano aluminum oxide and nano zinc oxide.
2. The method for preparing nano metal oxide modified thermal expansion microspheres of claim 1, wherein the method comprises the following steps: the particle size of the nanometer metal oxide modified thermal expansion microsphere is 5.5-55 mu m.
3. The method for preparing nano metal oxide modified thermal expansion microspheres of claim 1, wherein the method comprises the following steps: the saturated saline is one or a mixture of magnesium sulfate and sodium chloride.
4. The method for preparing nano metal oxide modified thermal expansion microspheres of claim 1, wherein the method comprises the following steps: the emulsifier is one or a mixture of NP-10, OP-10 or Tween-80; the wetting agent is one or a mixture of diisobutyl naphthalene sulfonate, dialkyl succinate sodium sulfonate, 2-ethylhexanol polyoxyethylene ether phosphate, methylene dinaphthalene sodium sulfonate or dodecyl alcohol polyoxyethylene ether; the emulsifying dispersant is one or a mixture of polyvinyl alcohol, sodium pyrophosphate, nano silicon dioxide, polyvinylpyrrolidone, trisodium phosphate, sodium dihydrogen phosphate or hydrotalcite.
5. The method for preparing nano metal oxide modified thermal expansion microspheres of claim 1, wherein the method comprises the following steps: the pH regulator is one or more of hydrochloric acid, succinic acid, adipic acid, citric acid, salicylic acid or tartaric acid 20-25 wt.%.
6. The method for preparing nano metal oxide modified thermal expansion microspheres of claim 1, wherein the method comprises the following steps: the functional water-soluble monomer is one or a mixture of methacrylamide, dimethylacrylamide, dimethylaminoethyl acrylate, dimethyl diallyl ammonium chloride or methacryloyloxyethyl trimethyl ammonium chloride; the functional oil-soluble monomer is one or a mixture of N-phenyl maleimide, N-dimethylacrylamide, vinyl trichlorosilane or gamma-chloropropyl trichlorosilane.
7. The method for preparing nano metal oxide modified thermal expansion microspheres of claim 1, wherein the method comprises the following steps: the low boiling point liquid is one or a mixture of more of n-butane, isobutane, isooctane, isopentane or petroleum ether.
8. The method for preparing nano metal oxide modified thermal expansion microspheres of claim 1, wherein the method comprises the following steps: the cross-linking agent is one or a mixture of dipentaerythritol hexaacrylate, hexanediol diacrylate, dimethylaminoethyl acrylate, ethylene glycol dimethacrylate, butanediol dimethacrylate or trimethylolpropane triacrylate.
9. The method for preparing nano metal oxide modified thermal expansion microspheres of claim 1, wherein the method comprises the following steps: the redox initiator consists of an oxidizing agent and/or a reducing agent; the oxidant is one or more of persulfate, peroxyacid salt or alkali metal peroxide; the reducing agent is one or more of sulfurous acid and salts thereof, bisulfite, thiosulfate, formaldehyde sulfoxylate, pyrosulfite alkali metal salts or pyrobisulfite.
CN201910712346.7A 2019-08-02 2019-08-02 Preparation method of nano metal oxide modified thermal expansion microspheres Active CN110372817B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910712346.7A CN110372817B (en) 2019-08-02 2019-08-02 Preparation method of nano metal oxide modified thermal expansion microspheres

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910712346.7A CN110372817B (en) 2019-08-02 2019-08-02 Preparation method of nano metal oxide modified thermal expansion microspheres

Publications (2)

Publication Number Publication Date
CN110372817A CN110372817A (en) 2019-10-25
CN110372817B true CN110372817B (en) 2021-11-09

Family

ID=68257834

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910712346.7A Active CN110372817B (en) 2019-08-02 2019-08-02 Preparation method of nano metal oxide modified thermal expansion microspheres

Country Status (1)

Country Link
CN (1) CN110372817B (en)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111995792B (en) * 2020-09-04 2022-08-23 陶光明 High-performance physical foaming agent and preparation method thereof
CN112876729B (en) * 2021-01-25 2023-02-17 唐山开滦化工科技有限公司 Magnetic thermal expansion microcapsule and preparation method and application thereof
CN112831082A (en) * 2021-01-29 2021-05-25 高密浩翰木塑材料科技有限公司 Production process of physical foaming agent for PVC foamed sole
CN114560965B (en) * 2022-02-25 2023-12-22 苏州仁端生物医药科技有限公司 Preparation method and application of nanoscale cationic carboxyl latex microspheres
CN115746377B (en) * 2022-11-21 2023-11-21 广东聚慧科技有限责任公司 High-temperature-resistant self-crosslinking thermal expansion microsphere and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004058910A1 (en) * 2002-12-25 2004-07-15 Matsumoto Yushi-Seiyaku Co., Ltd. Thermally expandable microcapsule, process for producing molded foam, and molded foam
CN104379647A (en) * 2012-09-04 2015-02-25 西能化工科技(上海)有限公司 Heat-expandable microspheres, preparation method and use thereof
CN107501595A (en) * 2017-08-23 2017-12-22 成都新柯力化工科技有限公司 A kind of method of non-melt state expanded polypropylene plastics
CN109134782A (en) * 2018-07-17 2019-01-04 西能化工科技(上海)有限公司 Low temperature microspheres and its preparation method and application
CN109456506A (en) * 2018-11-07 2019-03-12 西能化工科技(上海)有限公司 The heat-expandable microsphere and preparation method thereof of low residual monomer content

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004058910A1 (en) * 2002-12-25 2004-07-15 Matsumoto Yushi-Seiyaku Co., Ltd. Thermally expandable microcapsule, process for producing molded foam, and molded foam
CN104379647A (en) * 2012-09-04 2015-02-25 西能化工科技(上海)有限公司 Heat-expandable microspheres, preparation method and use thereof
CN107501595A (en) * 2017-08-23 2017-12-22 成都新柯力化工科技有限公司 A kind of method of non-melt state expanded polypropylene plastics
CN109134782A (en) * 2018-07-17 2019-01-04 西能化工科技(上海)有限公司 Low temperature microspheres and its preparation method and application
CN109456506A (en) * 2018-11-07 2019-03-12 西能化工科技(上海)有限公司 The heat-expandable microsphere and preparation method thereof of low residual monomer content

Also Published As

Publication number Publication date
CN110372817A (en) 2019-10-25

Similar Documents

Publication Publication Date Title
CN110372817B (en) Preparation method of nano metal oxide modified thermal expansion microspheres
CN105254817B (en) The preparation method of nucleocapsid esters of acrylic acid foaming control agent
JP2007526940A (en) Preparation of foam material from high internal phase emulsion
CN104893155B (en) PVC flooring base material and preparation method thereof
EP3284761A1 (en) Vinyl chloride-based polymer, preparation method therefor, and thermoplastic resin composition containing same
CN108084324B (en) Preparation method of high-strength special-shaped poly (methyl) acrylimide foam
JP6661703B2 (en) Method for producing acrylic copolymer, acrylic copolymer, and resin composition containing the same
KR20130112655A (en) Composition comprising crosslinked polymer nanoparticle, method for preparing thereof, and form forming property-reinforced pvc obtained from thereof
KR102081763B1 (en) Acrylic processing aid and vinyl chloride resin composition containing thereof
KR101056931B1 (en) Acrylic copolymer for processing aid of vinyl chloride-based resin composition, method for preparing the same, and vinyl chloride-based resin composition comprising the same
CN112940168A (en) Production process of high-viscosity PVC foaming regulator
US10640636B2 (en) Acrylic processing aid, method for preparing the same and polyvinylchloride resin composition comprising the same
CN105085773A (en) Polyacrylate polybasic copolymer with interpenetrating polymer network structure and preparation method thereof
CN103351562A (en) Multicomponent polymer for rigid polyvinyl chloride and preparation method of multicomponent polymer
KR101411098B1 (en) Method of preparing polyvinyl chloride comprising butyl acrylate
KR101997521B1 (en) Acrylic processing material, preparation method thereof and vinyl chloride resin composition comprising the same
JP6960000B2 (en) Method for producing graft copolymer
CN100572410C (en) A kind of preparation method who is used for the ABS resin of PVC soft sheet material
CN104327210A (en) Preparation of high-viscosity foaming-type modifier ACR (acrylate resin)
CN112778453B (en) Production process of acrylate processing aid for PVC soft sole
KR102464782B1 (en) Acrylic copolymer composition, method for preparing the copolymer composition and resin composition comprising the copolymer composition
KR20150050079A (en) Acrylic processing aid composition and vinyl chloride resin composition containing thereof
KR102105471B1 (en) Acrylic processing aid and vinyl chloride resin composition containing thereof
CN116082765B (en) Polyvinyl chloride foaming material with low dimensional change rate and high hardness and preparation method thereof
KR102652167B1 (en) Method for preparing acrylic processing aid, acrylic processing aid produced by the method and vinyl chloride resin composition comprising the acrylic processig aid

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
CB02 Change of applicant information
CB02 Change of applicant information

Address after: 261500 Renhe Community Industrial Park, Gaomi City Town, Gaomi City, Shandong

Applicant after: Shandong Yuanbang New Material Co.,Ltd.

Address before: 261500 Renhe Community Industrial Park, Gaomi City Town, Gaomi City, Shandong

Applicant before: GAOMI HAOHAN WOOD PLASTIC MATERIAL TECHNOLOGY Co.,Ltd.

GR01 Patent grant
GR01 Patent grant
CP01 Change in the name or title of a patent holder
CP01 Change in the name or title of a patent holder

Address after: 261500 Renhe Community Industrial Park, Gaomi City Town, Gaomi City, Shandong

Patentee after: Shandong Yuanbang New Material Co.,Ltd.

Address before: 261500 Renhe Community Industrial Park, Gaomi City Town, Gaomi City, Shandong

Patentee before: Shandong Yuanbang New Material Co.,Ltd.

PE01 Entry into force of the registration of the contract for pledge of patent right
PE01 Entry into force of the registration of the contract for pledge of patent right

Denomination of invention: A preparation method of nano metal oxide modified thermal expansion microspheres

Effective date of registration: 20231026

Granted publication date: 20211109

Pledgee: Rizhao Bank Co.,Ltd. Weifang Gaomi sub branch

Pledgor: Shandong Yuanbang New Material Co.,Ltd.

Registration number: Y2023980062829