CN106220887B - Expandable copolymer resin and preparation method thereof - Google Patents

Expandable copolymer resin and preparation method thereof Download PDF

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Publication number
CN106220887B
CN106220887B CN201610745735.6A CN201610745735A CN106220887B CN 106220887 B CN106220887 B CN 106220887B CN 201610745735 A CN201610745735 A CN 201610745735A CN 106220887 B CN106220887 B CN 106220887B
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mix monomer
temperature
mma
foaming agent
dispersant
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CN106220887A (en
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徐鑫
何凯锴
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    • 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
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/141—Hydrocarbons
    • 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
    • C08F212/00—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
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/08—Copolymers of styrene
    • C08L25/14—Copolymers of styrene with unsaturated esters
    • 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
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • 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
    • C08J2325/08—Copolymers of styrene
    • C08J2325/14—Copolymers of styrene with unsaturated esters
    • 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
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/14—Applications used for foams

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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)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

The invention discloses a kind of expandable copolymer resin and preparation method thereof, for this method using first polymerizeing, midway adds " method of a step half " of foaming agent so that polymerization initial stage avoids the inhibition of foaming agent, and average relative molecular mass is high, and mold strength is high；And polymerization rate is uniform, particle diameter distribution is narrow；Product yield is high；Waste water is disposable；Surface smoothness and the combination property of carbon residue are best.

Description

Expandable copolymer resin and preparation method thereof
Technical field
This belongs to lost foam casting material manufacture neck the present invention relates to a kind of expandable copolymer resin and preparation method thereof Domain.
Background technology
Technology of EPC is to use foamed plastics（EPS, STMMA or EPMMA）It is made and casting structure, size complete one The apperance of sample, cohere coating through dip-coating fire resisting（Play reinforcing, bright and clean）Special sandbox dry moulding is embedded to after drying, it is therein Coating plays reinforcing, bright and clean.Add negative pressure consolidation through three-dimensional or two-dimentional microseism, without loam core, the loose piece even situation without rising head Under pour into the aluminium alloy of fusing, whole process remains certain negative pressure, apperance is decomposed and then is taken by aluminium alloy by thermal evaporation The disposal molding New Casting Technique in generation.Lost foam casting has a variety of different calls, domestic mainly to cry dry sand cavityless casting, bear It is compacted mold casting, abbreviation EPC castings.External call mainly has lost foam process（The U.S.）、policast Process (Italy) etc..It has very big advantage compared with traditional foundry engieering, is described as by casting circle both domestic and external " foundry engieering of 21 century " and " green revolution of foundary industry ".
The Technology of EPC of China is also promoted by state key, and evaporative pattern industry is provided with certain scale, turns into The important component of casting industry, production casting proportion in casting industry improve constantly, and lost foam casting is current One of state-of-the-art casting technique in the world.
Compared with conventional casting technologies, lost foam casting has following features：
1. equipment investment can reduce 30-50%, casting quality is good, and casting cost can reduce 10-30%；
2. can production technology content is high, difficulty is big Near net shape, precise forming product；
3. product design has the bigger free degree, the personalized needs of following people have been adapted to；
4. internal defect in cast greatly reduces, dense structure；
5. extensive, high-volume, automatic assembly line production can be realized；
6. clean manufacturing can be realized, promote environmental protection and social sustainable development.
The special bead of lost foam casting has tri- kinds of EPS, STMMA, EPMMA, and its phosphorus content is reduced successively.
1. Expandable polystyrene resin bead（Abbreviation EPS）；
2. expandability methyl methacrylate and styrene copolymerized resin bead（Abbreviation STMMA）；
3. expandability plexiglass bead（Abbreviation EPMMA）.
1, of subordinate list, tri- kinds of beads contrast in lost foam casting industry service condition
For expandability methyl methacrylate and styrene copolymerized resin bead STMMA, typically using one-step method, that is, exist Monomer polymerization stage adds the foaming agents such as pentane.Polymerization of the foaming agents such as pentane to styrene and methyl methacrylate has Inhibition, this is caused, and molecular weight of copolymer is relatively low, particle diameter distribution is wide, and molecular weight is low when directly resulting in resin as cast material The problems such as low intensity, and particle diameter distribution is wide, then the less powder of particle diameter at most causes product yield low.In addition, one-step method system It is big usually using organic dispersing agent, caused wastewater treatment difficulty during standby STMMA.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of expandable copolymer resin and preparation method thereof, solve existing Bead granular diameter distribution is wide in one-step method, two material is more, product yield is low, molecular weight is low, cast material low intensity, wastewater treatment are difficult Spend big problem.
Meanwhile the present invention is investigated in STMMA the ratio between styrene and MMA to surface smoothness in cast material With the influence of carbon residue, appropriate scope is have chosen, is considered in the influence factor shifting from two, this is prior art In from unwitnessed.
In order to solve the above problems, the present invention adopts the following technical scheme that：
A kind of expandable copolymer resin, in parts by weight, its raw material include mix monomer 100, deionized water 120-300, Dispersant 0.2-0.8, foaming agent 7-12, initiator 0.3-0.8, modified additive 0.03-0.2.
Wherein, mix monomer is by styrene (ST) and methyl methacrylate（MMA）Form, with the weight of mix monomer 100 Part meter, ST:MMA=99:1-1:99, preferably 65:35-85:15, more preferably 70:30-80:20, most preferably 75:25-80:20, most Good value is 75:25.
Wherein, dispersant uses inorganic dispersant, such as active calcium phosphate (TCP).
Wherein, foaming agent is C4-C6 low boiling hydrocarbon compounds.
Wherein, modified additive is Tissuemat E, dioctyl phthalate (DOP).
The invention further relates to the preparation method of the expandable copolymer resin：
Low temperature polymerization reaction is carried out after deionized water, mix monomer, dispersant, initiator, modified additive are mixed, is reached After the defined low temperature polymerization reaction time, foaming agent is added, carries out high temperature reaction, after reaching the defined reaction time, cooling To defined temperature.
Wherein, methods described also includes：After cooling, then centrifuge washing, drying, screening, coating, finished product bag are carried out respectively Dress.
Wherein, methods described concretely comprises the following steps：Deionized water, mix monomer, dispersant, initiator, modified additive are mixed Low temperature polymerization is carried out after conjunction, polymerization temperature is 60-100 DEG C, after reaching defined 4-10 hours in low temperature polymerization reaction time, is added Foaming agent, high temperature reaction is carried out, reaction temperature is 90-130 DEG C, pressure 0.4-0.9 MPa, reaches defined reaction time 4- After 10 hours, temperature≤50 DEG C are cooled to.
The beneficial effects of the invention are as follows：Because using first polymerizeing, midway adds " method of a step half " of foaming agent, polymerization initial stage It is high to avoid the inhibition average relative molecular mass of foaming agent, mold strength height；Polymerization rate is uniform, particle diameter distribution It is narrow；Product yield is high；Waste water is disposable；Surface smoothness and the combination property of carbon residue are best.
According to the accompanying drawings will be brighter to the detailed description of the specific embodiment of the invention, those skilled in the art Above-mentioned and other purposes, the advantages and features of the present invention.
Brief description of the drawings
Some specific embodiments of the present invention are described in detail by way of example, and not by way of limitation with reference to the accompanying drawings hereinafter. Identical reference denotes same or similar part or part in accompanying drawing.It should be appreciated by those skilled in the art that these What accompanying drawing was not necessarily drawn to scale.In accompanying drawing：
Fig. 1 is one-step method STMMA technological process of production block diagrams.
Fig. 2 is the method STMMA technological process of production block diagrams of a step half of invention.
Embodiment
Embodiment 1：
In parts by weight, mix monomer 100, deionized water 300, dispersant 0.4, foaming agent 9, initiator 0.3, modification are taken Auxiliary agent 0.05.Mix monomer is by styrene (ST) and methyl methacrylate（MMA）Form, ST: MMA = 75 : 25;Hair Infusion is C4 ~ C6 low boiling hydrocarbon compounds；Modified additive is Tissuemat E；Dispersant uses inorganic dispersant active calcium phosphate (TCP)。
Low temperature polymerization, polymerization temperature are carried out after deionized water, mix monomer, dispersant, initiator, modified additive are mixed 80 DEG C, after reaching the defined 8 hours low temperature polymerization reaction time, foaming agent is added, carries out high temperature reaction, reaction temperature 100 DEG C, pressure 0.4MPa or so, after reaching the defined 8 hours reaction time, it is cooled to defined temperature（≤50℃）Afterwards, then distinguish Carry out centrifuge washing, drying, screening, coating, finished product packing.
Embodiment 2
ST : MMA =70:30, remaining condition is same as Example 1.
Embodiment 3
ST : MMA =65:35, remaining condition is same as Example 1.
Embodiment 4
ST : MMA =80:20, remaining condition is same as Example 1.
Comparative example 1：
Using one-step method, i.e.,：
In parts by weight, mix monomer 100, deionized water 300, dispersant 0.4, foaming agent 9, initiator 0.3, modification are taken Auxiliary agent 0.05.Mix monomer is by styrene (ST) and methyl methacrylate（MMA）Form, ST: MMA = 75 : 25;Hair Infusion is C4 ~ C6 low boiling hydrocarbon compounds；Modified additive is Tissuemat E；Dispersant uses inorganic dispersant active calcium phosphate (TCP)。
It is polymerize after deionized water, mix monomer, dispersant, initiator, modified additive and foaming agent are mixed, is polymerize Temperature:90 DEG C, MPa of pressure 0.4 or so, after reaching the defined 16 hours reaction time, it is cooled to defined temperature（≤50℃） Afterwards, then respectively centrifuge washing, drying, screening, coating, finished product packing are carried out.
Comparative example 2：
Using the method for a step half, but ST: MMA =55:45, remaining condition is same as Example 1.
Comparative example 3：
Using the method for a step half, but ST: MMA =90:10, remaining condition is same as Example 1.
The ash determination of the carbon residue of embodiment 5
The product that will be obtained after resinous coat obtained by embodiment 1-4 and comparative example 2-3, using GB/T 9345.1-- 2008/IS0 3451-1：1997 standards,《The measure part 1 of plastics ash content：Universal method》Described in method, use Condition is 950 DEG C of Muffle furnace temperature control, 50 DEG C of soil.Sample 50g, calcination time 30min.
The ash determination of table 2.
Embodiment 6
The product that will be obtained after resinous coat obtained by embodiment 1-4 and comparative example 2-3, by prefoam, drying, ripe Change, after shaping, using identical mould, carry out disappearance molding, then product surface finish is evaluated.Cast member is bright and clean No corresponding national standard is spent, therefore the standard of marking is estimated using technical staff, is 10 as minute surface is bright and clean, it is thick such as sand paper Rough is 1.
The finish of table 3.
Integrated embodiment 5-6 result, when within the scope of the invention, particularly ST: MMA =70:30-80:20 In the range of, carbon residue and surface smoothness are best.Comparative example 1 and comparative example 1, can be obtained as drawn a conclusion.
The conclusion of table 4.
So far, although those skilled in the art will appreciate that detailed herein have shown and described multiple showing for the present invention Example property embodiment, still, still can be direct according to present disclosure without departing from the spirit and scope of the present invention It is determined that or derive many other variations or modifications for meeting the principle of the invention.Therefore, the scope of the present invention is understood that and recognized It is set to and covers other all these variations or modifications.

Claims (3)

1. a kind of expandable copolymer resin, in parts by weight, its raw material include mix monomer 100, deionized water 120-300, divided Powder 0.2-0.8, foaming agent 7-12, initiator 0.3-0.8, modified additive 0.03-0.2;
Mix monomer is by styrene (ST) and methyl methacrylate（MMA）Form, in terms of the parts by weight of mix monomer 100, ST: MMA= 75:25-70:30;
The preparation method of described copolymer resins concretely comprises the following steps：By deionized water, mix monomer, dispersant, initiator, modification Low temperature polymerization is carried out after auxiliary agent mixing, polymerization temperature is 60-100 DEG C, reaches defined 4-10 hours in low temperature polymerization reaction time Afterwards, foaming agent is added, carries out high temperature reaction, reaction temperature is 90-130 DEG C, pressure 0.4-0.9 MPa, reaches defined anti- Between seasonable after 4-10 hours, temperature≤50 DEG C are cooled to；After cooling, then respectively carry out centrifuge washing, drying, screening, coating, into Product are packed；
The dispersant uses inorganic dispersant active calcium phosphate (TCP)；
The foaming agent is C4-C6Low boiling hydrocarbon compound;
The modified additive is Tissuemat E, dioctyl phthalate (DOP).
2. copolymer resins as claimed in claim 1, it is characterised in that mix monomer is by styrene (ST) and methyl methacrylate Ester（MMA）Form, in terms of the parts by weight of mix monomer 100, ST:MMA= 75:25.
3. a kind of preparation method of the copolymer resins described in claim 1-2, is concretely comprised the following steps：By deionized water, mix monomer, Low temperature polymerization is carried out after dispersant, initiator, modified additive mixing, polymerization temperature is 60-100 DEG C, reaches defined low temperature and gathers After closing hour in reaction time 4-10, foaming agent is added, carries out high temperature reaction, reaction temperature is 90-130 DEG C, pressure 0.4-0.9 MPa, after reaching defined hour in reaction time 4-10, it is cooled to temperature≤50 DEG C;After cooling, then respectively carry out centrifuge washing, Drying, screening, coating, finished product packing;
Its raw material includes mix monomer 100, deionized water 120-300, dispersant 0.2-0.8, foaming agent 7-12, initiator 0.3- 0.8th, modified additive 0.03-0.2;
Mix monomer is by styrene (ST) and methyl methacrylate（MMA）Form, in terms of the parts by weight of mix monomer 100, ST: MMA= 75:25-70:30。
CN201610745735.6A 2016-08-29 2016-08-29 Expandable copolymer resin and preparation method thereof Ceased CN106220887B (en)

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CN106220887B true CN106220887B (en) 2017-11-10

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Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102911307B (en) * 2012-09-20 2015-07-22 宁波新桥化工有限公司 Expandable copolymer resin and method for preparing same
CN104311867B (en) * 2014-10-27 2017-11-14 武汉工程大学 A kind of preparation method of catalytic gasification disappearance mold foam

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