CN107254021A - A kind of regenerating and modifying method of thermosetting unsaturated polyester resin waste - Google Patents
A kind of regenerating and modifying method of thermosetting unsaturated polyester resin waste Download PDFInfo
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- CN107254021A CN107254021A CN201710472504.7A CN201710472504A CN107254021A CN 107254021 A CN107254021 A CN 107254021A CN 201710472504 A CN201710472504 A CN 201710472504A CN 107254021 A CN107254021 A CN 107254021A
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- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
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- 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
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- 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
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
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- 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
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
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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
- C08L51/08—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 otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
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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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/06—Unsaturated polyesters
Abstract
The invention discloses a kind of regenerating and modifying method of thermosetting unsaturated polyester resin waste, using thermosetting unsaturated polyester resin waste particle as modified substrate, using acrylic ester monomer as modified monomer, under conditions of the presence of 80~100 DEG C, catalyst and alcoholysis agent, scattered 30~the 180min of shearing is carried out in aqueous dispersions using high-shear emulsifying dispersing apparatus, and by suspension polymerisation or emulsion polymerization, it is filtrated to get modified heat convertible unsaturated polyester resin；The particle diameter of the modified substrate is 200~600 mesh；The catalyst is the one or more in the alkene of 1,5,7 three azabicyclic [4.4.0] last of the ten Heavenly stems 5, zinc acetylacetonate and zinc acetate；The alcoholysis agent is the one or more in water, alcohol and carboxylic acid.The method that the regenerating and modifying method of the present invention utilizes conventional polymeric, in the case of a small amount of equipment investment, the regenerating and modifying of large-scale thermosetting unsaturated polyester resin waste can be carried out, modified cost is low, and can be modified as being molded directly into the new high molecular polymer of thermoplasticity of type.
Description
Technical field
The present invention relates to field of new materials, more particularly to a kind of regenerating and modifying side of thermosetting unsaturated polyester resin waste
Method.
Background technology
Thermosetting resin accounts for the 15% of whole quantity of plastics.Thermosetting resin after completion of cure, it is not molten, insoluble with it
Property, as it is a kind of can not regeneration polymeric scrap, and usually and be classified as because wherein containing a small amount of organic volatile
Dangerous debirs, abbreviation dangerous waste.Thermosetting resin waste material is always that a kind of processing cost is high (burning), and is difficult to recycle
High-molecular compound.But, with the development of thermosetting resin industry, domestic usage amount is increasing.According to " middle Guohe
Unsaturated-resin in the statistics of unsaturated-resin employer's organization of resin association ", thermosetting resin just reached in 2015
To 2,100,000 tons, also slightly going up within 2016.The service life of this resinoid is general indoor 10~20 years, outdoor 6~10 years,
But usually the shorter time has just scrapped, waste material over the years, redundancy material, retired product etc., thermosetting resin waste material are added
Amount be astronomical figure.
All the time, thermosetting resin waste material is all the thermosetting resin component based on the processing method that fills and burn
More complicated, natural degradation is slow, thus landfill impacts to environment；And when being carried out environmentally friendly burning disposal, cost is higher,
Processing cost per ton is at 2000 yuan or so.So seek it is other efficiently, environmental protection, easily processing method it is very urgent.
Application No. CN200610123929.9 Chinese patent literature discloses a kind of unsaturated polyester button and technique
Product waste material is used for the method for modified plastics, comprises the following steps：(1) unsaturated polyester button and handicraft wasted powder and plastics
Mixing, makes the wasted powder be dispersed in plastics, obtains unsaturated polyester (UP) powder modification plastic hybrid, plastics are with giving up
The mass ratio at feed powder end is 40~95: 5~60；(2) the mixture shaping that step (1) is obtained, obtains unsaturated polyester (UP) powder and changes
Property plastics.The patent is adulterated button powder as a kind of organic filler in fact, and unsaturated-resin performance itself fails just really to change
Property plasticizing, so market value is smaller.
Application No. CN201110060899.2 Chinese patent literature discloses a kind of time for scrapping thermosetting plastics part
Reproducing method is received, the nonmetal parts of first demolishing and scrapping machinery sub-elect thermosetting/thermoplastic plastic parts and crushed；Again by unsaturated polyester (UP)
Resin, peroxidized t-butyl perbenzoate, zinc stearate dispersion mixing, sequentially add thermosetting plastics powder and thermoplastic is obtained
The short glass fiber arrived is mixing cured；Finally place into hydraulic press compression molding.This method is by thermoset automotive waste material generation
With unsaturated polyester (UP) it is adhesive for common inorganic filler, compression molding new casting, equipment cost is high, and processing cost is big.
The one kind disclosed in patent CN95106464.9 such as last century the nineties Japanese Kubo Tian Jingnan are to such as knob
The waste material of the unsaturated polyester resin waste produced in button manufacturing process or the article of fiber reinforced plastics containing glass fibre is carried out
It is chemically treated to obtain the renovation process and its device of industrial useful raw material.That is, with dihydric alcohol degraded unsaturated polyester (UP) tree
Fat waste material, is made the raw material containing dihydric alcohol.The degraded to be advisable under elevated pressure.Can be by making the above-mentioned raw material containing dihydric alcohol
Reacted with unsaturated dibasic acid and monounsaturated dicarboxylic acid, synthesize unsaturated polyester resin.Also can by make raw material containing dihydric alcohol with
Diisocyanate cpd reacts synthesis of polyurethane resin.The requirement of this technical requirements degradation condition and equipment is high, and production of degrading
Raw product component is complicated, is not readily separated utilization.
The content of the invention
For asking of solving that the thermosetting unsaturated polyester resin waste after existing solidification is unable to that effective regeneration recycles
Topic, the invention provides a kind of regenerating and modifying method of thermosetting unsaturated polyester resin waste, passes through changing that this method is obtained
Property thermosetting unsaturated polyester resin has good plasticity, and can repeat plasticizing forming.
A kind of regenerating and modifying method of thermosetting unsaturated polyester resin waste, with thermosetting unsaturated polyester resin waste
Particle is modified substrate, using acrylic ester monomer as modified monomer, the bar existed in 80~100 DEG C, catalyst and alcoholysis agent
Under part, the scattered 30~180min of shearing is carried out in aqueous dispersions using high-shear emulsifying dispersing apparatus, and pass through suspension polymerisation
Or emulsion polymerization, it is filtrated to get modified heat convertible unsaturated polyester resin；
The particle diameter of the modified substrate is 200~600 mesh；
The catalyst is one kind in 1,5,7- tri- azabicyclic [4.4.0] decyl- 5- alkene, zinc acetylacetonate and zinc acetate
Or it is a variety of；
The alcoholysis agent is the one or more in water, alcohol and carboxylic acid.
Thermosetting unsaturated polyester resin has the network structure using ester bond as crosslink unit, so as to macroscopically see, is crosslinked
Unsaturated polyester resin there is molecular flexibility, its segment is changed by occurred conformation after force-extension, system's entropy is reduced and is located
In high-energy level, this change turns to interim elastic deformation；Remove after external force, strand will be returned to the minimum structure of original ability
As system is also correspondingly returned to original shape.So, this cross-linked elastomer system can not be reprocessed into other shapes
Shape.In the presence of ester exchange catalyst, its cross-linked structure can be interrupted by water, small molecular alcohol or small molecule acid, make network structure
Linear polymeric is degraded into, is shown below, after network degraded, linear polymer segment occurs no longer under external force
It is conformation change, but the frictional slip of molecule interchain so that system is plastically deformed；Remove after external force, system's entropy is constant
And ability minimum state is in all the time.Polymer Systems can finally had and re-works/the performance of reuse.
In the regenerating and modifying method of the present invention, under conditions of catalyst, water, alcohol or acid are present, pass through high temperature high shear
Thermosetting unsaturated polyester resin is set to dredge chain, catalyst, water, alcohol enter inside thermosetting unsaturated polyester resin so that thermosetting
Property unsaturated polyester (UP) dredge chain under high shear, and make subnetwork ester linkage breaking, occur with small molecular alcohol, acid or esters of acrylic acid
Ester exchange reaction, so that further solution crosslinking；In this way, not only significantly reducing the crosslink density of primary resin, strand is set to produce
Raw draw is moved, and under the plasticising lubrication of its surface grafting acrylic polymer so that polymer-modified final energy
Enough plasticizing processing.
Regenerating and modifying method by the present invention is modified, thermosetting unsaturated polyester resin and acrylic ester monomer it
Between polymerize, change thermosetting unsaturated polyester resin recurring structure, rather than thermosetting unsaturated polyester resin and third
Mutual doping between olefin(e) acid esters monomer, so minimal amount of acrylic ester monomer (be less than modified substrate 10%) can be used
And cause modified polymer that there is good plasticity, and plasticizing forming can be repeated.Because thermosetting unsaturation is poly-
The grain diameter of ester resin is thinner, and its oil factor is higher, if by thermosetting unsaturated polyester resin and a small amount of esters of acrylic acid
The simple mutually doping of monomer (be less than modified substrate 10%), acrylic ester monomer can not be by thermosetting unsaturated polyester resin
Powder bonding, reaches the purpose of compression molding.
Preferably, the rotating speed of high-shear emulsifying dispersing apparatus is 6000~20000 revs/min.
When carrying out shearing scattered using high-shear emulsifying dispersing apparatus, the temperature of aqueous dispersions can be raised constantly, in order to protect
The temperature of water holding dispersion liquid is in the range of 80~100 DEG C, high-shear emulsifying dispersing apparatus periodic running, and each run 5~
10min, is spaced 2~3min.
In the regenerating and modifying method of the present invention, the modified particle surface for typically occurring in modified substrate, so modified base
The particle diameter at bottom is smaller more more effectively to occur surface modification, so that more preferable plasticizing effect is obtained, preferably, the modification
The particle diameter of substrate is 200~400 mesh；It is further preferred that the particle diameter of the modified substrate is 200~300 mesh.
Preferably, described modified monomer be acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate,
Ethyl acrylate, EMA, butyl acrylate, butyl methacrylate, Isooctyl acrylate monomer, vinyl acetate,
One or more in long alkyl chain acrylate, propylene cyanogen and styrene.
It is further preferred that in mass, the consumption of described modified monomer is the 5~200% of modified substrate quality；Enter
One step is preferred, and the consumption of described modified monomer is the 5~25% of modified substrate quality.
Occur ester exchange at the avtive spot of the modified substrate of above-mentioned modified monomer on the one hand after catalytic activation, make part
The network structure of thermosetting unsaturated polyester resin is changed into the linear chain structure of slip, makes modified thermosetting insatiable hunger
There is plasticity with polyester resin；On the other hand, modified monomer plays a part of lubrication to linear chain structure, can further increase
The plasticity of thermosetting unsaturated polyester resin after additivity.
The main function of catalyst in the present invention be open molecule segment in ester bond there is provided ester exchange avtive spot,
It is not intended to thermosetting unsaturated polyester resin of thoroughly degrading.
Preferably, the quality of described catalyst is the 0.1~1.5% of modified substrate quality；It is further preferred that institute
The quality for the catalyst stated is the 0.5~1% of modified substrate quality.
Preferably, described alcoholysis agent is the one or more in water, ethylene glycol and propane diols.
Alcoholysis agent is reacted at ester exchange avtive spot with thermosetting unsaturated polyester resin, destroys its network structure, is dropped
Its low molecular weight.
The regenerating and modifying method of the present invention can use suspension polymerisation or emulsion polymerization.
During using suspension polymerisation, comprise the following steps：
(1) modified substrate, alcoholysis agent and catalyst are added in aqueous dispersions, using high shear breast at 80~100 DEG C
Change dispersing apparatus and carry out the scattered 30~180min of shearing, catalytic activation modified substrate；
(2) aqueous dispersions, initiator and modified monomer are added into the slurry of the modified substrate after catalytic activation, 80~
100 DEG C of low suspension polymerizations, cold filtration obtains modified heat convertible unsaturated polyester resin.
The purpose that high shear is stirred under high temperature is positive opening thermosetting unsaturated polyester resin, makes alcoholysis agent and catalyst
Enter inside thermosetting unsaturated polyester resin, catalyst makes to produce avtive spot inside thermosetting unsaturated polyester resin,
At avtive spot with thermosetting unsaturated polyester resin ester exchange occurs for alcoholysis agent, breaks heat exchange solidity unsaturated polyester resin
Network structure, is convenient for the modification of subsequent step, and the time of high shear stirring can not make thermosetting unsaturated polyester (UP) when too short
Resin is effectively activated, and its activation efficiency is reduced during the overlong time of high shear stirring, preferably, in step (1), cutting
The cutting scattered time is 30~60min.
Preferably, in step (2), the temperature of suspension polymerisation is 80~85 DEG C, time of suspension polymerisation for 120~
240min。
Preferably, in step (2), the filtrate of cold filtration is back to step (1) as aqueous dispersions.In step (2),
The filtrate of cold filtration can as next kettle regenerating and modifying aqueous dispersions, do not cause secondary pollution.
During using emulsion polymerization, comprise the following steps：
(I) modified substrate, alcoholysis agent, catalyst, emulsifying agent and modified monomer are added in aqueous dispersions, cut using height
Cut emulsion dispersion equipment and carry out the scattered 30~180min of shearing, obtain modified suspending emulsion；
(II) modified suspending emulsion is continuously added drop-wise in bottoming liquid, in 80~100 DEG C of emulsion polymerisations, cold filtration,
Obtain modified heat convertible unsaturated polyester resin.
Preferably, in step (I), the shearing scattered time is 30~60min.
Preferably, in step (II), the temperature of emulsion polymerization is 80~85 DEG C, time of emulsion polymerization for 120~
240min。
Preferably, the bottoming liquid described in step (II) is the aqueous solution containing emulsifying agent and initiator.
Filter to isolate after modified heat convertible unsaturated polyester resin, the breast with being added without thermosetting unsaturated polyester resin
Obvious change does not occur for liquid phase ratio, the performance of filtrate, i.e., emulsion polymerization does not influence the use value of former emulsion formulations.
Initiator described above is thermal polymerization.
Compared with prior art, beneficial effects of the present invention are：
The method that the regenerating and modifying method of the present invention utilizes conventional polymeric, in the case of a small amount of equipment investment, can be carried out
The regenerating and modifying of large-scale thermosetting unsaturated polyester resin waste, modified cost is low, and can be modified as energy directly
The new high molecular polymer of thermoplasticity of compression molding, with great economic value and social benefit.
Embodiment
Thermosetting unsaturated polyester (UP) waste residue used in following examples is the button tree that Jiashan Dong great resins Co., Ltd produces
Fat waste material, the waste material is resin solidification into the redundancy leftover pieces that button is produced after sheet material, is not melting after cured crosslinking, insoluble
Thing.After the present invention crushes the size-reduced machine of this redundancy waste material, ground with cement grinding mill under the conditions of water cooling, 300 mesh powder of final screening
Material is standby as modified matrix.Other raw materials and source such as following table：
The raw material of table 1 and source
Embodiment 1
By above-mentioned 200 kilograms of modified matrix, 300 kilograms of water, 5 kilograms of alcoholysis agent ethylene glycol, equipped with 20kw high shears breast
Change stirring in the enamel still of dispersion machine and be warming up to 80~90 DEG C, stirred batch is carried out, each run 5 minutes, is spaced 2min.Temperature
Spend to addition 0.8 kilogram of azabicyclic [4.4.0] the decyl- 5- alkene (TBD) of catalyst 1,5,7- tri- after 80 DEG C, in high shear agitation
Under be modified the surface activation of matrix, the catalytic activation time is 30~60min.
By after catalytic activation thermosetting resin discarded object slurry add 1 ton of enamel polymerization still, and add 140 kilograms of water,
0.8 kilogram of dispersant calcium hydroxy phosphate, 0.2 kilogram of initiator azodiisobutyronitrile, 10 kilograms of styrene (St), butyl acrylate
(BA) 20 kilograms, 80 DEG C are warming up to, suspension polymerisation is carried out in stirring, polymerisation 3 hours adds a small amount of TBHP
After be warming up to 85 DEG C, react 30 minutes, be cooled to less than 50 DEG C, spherical modified particles are considered from aqueous phase, plasticization is produced
Modified heat convertible resin.
Above-mentioned spherical modified particles are being dried, its moisture is less than 1%, 300 grams of particle for taking this to dry, certainly
Compression molding on dynamic powder compressing machine, carries out tensile strength of material test.
Embodiment 2
The present embodiment with when technique such as embodiment 1, it is unique unlike catalyst be zinc acetylacetonate.
Embodiment 3
The present embodiment with when technique such as embodiment 1, it is unique unlike catalyst be zinc acetate.
Embodiment 4
Embodiment 1 is isolated to the aqueous dispersions after modified heat convertible resin as dispersed phase (abbreviation water for convenience of explanation
Dispersion liquid).
200 kilograms of modified matrix is taken, 300 kilograms of aqueous dispersions, 2.7 kilograms of alcoholysis agent ethylene glycol is cut installing 20kw height
Cut stirring in the enamel still of emulsion dispersion machine and be warming up to 80~90 DEG C, stirred batch is carried out, each run 5 minutes, is spaced 2 points
Clock.Temperature carries out surface activation, soak time 30 to 0.8 kilogram of addition catalyst TBD after 80 DEG C under high shear agitation
~60min.
Thermosetting resin discarded object slurry after catalytic activation is added into 1 ton of enamel polymerization still, and adds aqueous dispersions 140
Kilogram, 0.8 kilogram of dispersant calcium hydroxy phosphate, 0.2 kilogram of initiator azodiisobutyronitrile, 10 kilograms of styrene (St), propylene
20 kilograms of acid butyl ester (BA), is warming up to 80 DEG C, and suspension polymerisation is carried out in stirring, and polymerisation 3 hours adds a small amount of tert-butyl group mistake
Hydrogen oxide heats up 85 DEG C, reacts 30 minutes, is cooled to less than 50 DEG C, spherical modified particles are considered from aqueous phase, you can obtain plastic
The modified heat convertible resin of change.
Above-mentioned spherical modified particles are being dried, its moisture is less than 1%, 300 grams of particle for taking this to dry, certainly
Compression molding on dynamic powder compressing machine, carries out tensile strength of material test.
Embodiment 5
The present embodiment with when technique such as embodiment 1, difference is modified monomer for 10 kilograms of styrene (St),
10 kilograms of methyl methacrylate (MMA).
Embodiment 6
Take 100 kilograms of modified matrix, 200 kilograms of water, 15 kilograms of butyl acrylate (BA), 37.5 kilograms of styrene (St),
5 kilograms of alcoholysis agent propane diols, 0.5 kilogram of catalyst TBD, 0.4 kilogram of emulsifying agent K-12,1.6 kilograms of polyoxyethylene nonylphenol ether/OS,
Install in the enamel still of 15kw high-shear emulsifying dispersion machines and stir, stirred batch is carried out, each run 5 minutes, be spaced 2 points
Clock.Soak time is 30 minutes, prepares modified suspending emulsion.
0.1 kilogram of emulsifying agent K-12,0.6 kilogram of polyoxyethylene nonylphenol ether/OS, bicarbonate are added in 500 liters of enamel polymerization stills
0.3 kilogram of sodium, 0.15 kilogram of ammonium persulfate and 123 kilograms of bottoming of water, and it is warming up to 80 DEG C, above-mentioned modified suspending emulsion is added dropwise,
And 25 kilograms of 2% persulfate solution is synchronously added dropwise.Modified suspending emulsion and persulfate solution are dripped off for 1.5 hours, are warming up to 85 DEG C
5 kilograms of 2% ammonium persulfate solution is added in insulation after 1 hour, cooling discharging after being incubated 0.5 hour.Granular precipitate is considered and baking
It is dry to produce modified heat convertible resin.
After above-mentioned spherical modified particles drying, its moisture is set to be less than 1%, 300 grams of particle for taking this to dry, in automatic powder
Compression molding on last tablet press machine, carries out tensile strength of material test.
Embodiment 7
Take 52.5 kilograms of modified matrix, 200 kilograms of water, 28.6 kilograms of BA, 71.4 kilograms of St, alcoholysis agent propane diols 2.5
Kilogram, 0.26 kilogram of catalyst TBD, 0.4 kilogram of emulsifying agent K-12,1.6 kilograms of polyoxyethylene nonylphenol ether/OS are cut installing 15kw height
Cut in the enamel still of emulsion dispersion machine and stir, stirred batch is carried out, each run 5 minutes, be spaced 2 minutes.Soak time 30
Minute, prepare modified suspending emulsion.
0.1 kilogram of K-12,0.6 kilogram of OP/OS, 0.3 kilogram of sodium acid carbonate, mistake are added in 500 liters of enamel polymerization stills
0.15 kilogram of ammonium sulfate and 123 kilograms of bottoming of water, and it is warming up to 80 DEG C, above-mentioned modified suspending emulsion is added dropwise, and be synchronously added dropwise 2%
25 kilograms of ammonium persulfate solution.Modified suspending emulsion and ammonium persulfate solution are dripped off for 1.5 hours, are warming up to 85 DEG C and are incubated 1 hour
After add 5 kilograms of 2% ammonium persulfate solution, cooling discharging after insulation 0.5 hour.Granular precipitate is considered and drying modification
Thermosetting resin；Emulsion breaking is obtained into polymer powder (polystyrene) simultaneously, clean, dry for standby.
After above-mentioned spherical modified particles and powdery resin drying, its moisture is set to be less than 1%, for taking this to dry respectively
Grain and each 300 grams of polymer powder, compression molding on each comfortable automatic Powder tablet press machine, carries out tensile strength of material survey respectively
Examination.
Comparative example 1
100 kilograms of water intaking, 28.6 kilograms of BA, 71.4 kilograms of St, 0.26 kilogram of emulsifying agent K-12, polyoxyethylene nonylphenol ether/OS
1.1 kilograms, stirred in the enamel still for installing 15kw high-shear emulsifying dispersion machines, stirred batch is carried out, 5 minutes every time.Breast
10 minutes change time, prepare pre-emulsion.
0.07 kilogram of K-12,0.4 kilogram of OP/OS, 0.3 kilogram of sodium acid carbonate, mistake are added in 500 liters of enamel polymerization stills
0.10 kilogram of ammonium sulfate, 100 kilograms of bottoming of water, and it is warming up to 80 DEG C, above-mentioned modified suspending emulsion is added dropwise, and be synchronously added dropwise 2%
25 kilograms of ammonium persulfate solution.Modified suspending emulsion and ammonium persulfate solution are dripped off for 1.5 hours, are warming up to 85 DEG C and are incubated 1 hour
After add 5 kilograms of 2% ammonium persulfate solution, cooling discharging after insulation 0.5 hour.Powder is dried into after above-mentioned emulsion is demulsified
Shape.
After above-mentioned polymer powder is dried, its moisture is set to be less than 1%, the polymer powder (polyphenyl for taking this to dry
Ethene) 300 grams, the compression molding on automatic Powder tablet press machine carries out tensile strength of material test.
Test example 1
Draftability performance is tested using Zwick/Roell Z020 (German Zwick companies) type universal testing machine, ginseng
According to GB/T1040-2006；
Test condition：Draw speed is 5mm/min.
Polymer powder in the moulding material of modified heat convertible unsaturated polyester resin and comparative example 1 in embodiment 1~7
The tensile strength test results of (polystyrene) moulding material are shown in Table 2.
The tensile strength test results of the material of compression molding in the embodiment 1~7 of table 2 and comparative example 1
The moulding material of polymer powder (polystyrene) and polymer powder (polyphenyl in comparative example 1 in embodiment 7
Ethene) tensile strength test results of moulding material are shown in Table 2.
In table 3, when being modified using the method for the present invention to thermosetting unsaturated polyester resin, modifying process
The property of modified monomer emulsion is not influenceed.
Influence of the modification of the thermosetting unsaturated polyester (UP) powder of table 3 to emulsion polymer tensile strength
| Try example | Embodiment 7 | Comparative example |
| Tensile strength (MPa) | 42.2 | 42.0 |
The grafting amount of modified monomer is shown in Table 4 on modified heat convertible unsaturated polyester resin in embodiment 6 and embodiment 7.
Table 4 activates influence of the unsaturated polyester (UP) powder to emulsion solid content
| Try example | Embodiment 6 | Embodiment 7 |
| Unsaturated polymer is activated to add | 100 | 52.5 |
| Emulsion polymerization sediment drying amount | 106.3 | 56.2 |
| It is grafted object amount (%) | 6.3 | 7 |
The method of modifying of the present invention is can be seen that from above test data, can cause thermosetting polymer is modified to have
Plasticity, can be molded directly into, and can plastify repeatedly.Its modified intensity has pure stretched polystyrene intensity
More than 80%, with higher economic value.And substantial amounts of thermosetting unsaturated polyester (UP) can be handled, environmental pollution is reduced, becomes useless
For treasured.
Claims (9)
1. a kind of regenerating and modifying method of thermosetting unsaturated polyester resin waste, it is characterised in that poly- with thermosetting unsaturation
Ester resin waste particle is modified substrate, using acrylic ester monomer as modified monomer, in 80~100 DEG C, catalyst and alcoholysis
Under conditions of agent is present, the scattered 30~180min of shearing is carried out in aqueous dispersions using high-shear emulsifying dispersing apparatus, and lead to
Suspension polymerisation or emulsion polymerization are crossed, modified heat convertible unsaturated polyester resin is filtrated to get；
The particle diameter of the modified substrate is 200~600 mesh；
The catalyst is 1,5,7- tri- azabicyclic [4.4.0] decyl- 5- alkene, zinc acetylacetonate and one kind or many in zinc acetate
Kind；
The alcoholysis agent is the one or more in water, alcohol and carboxylic acid.
2. the regenerating and modifying method of thermosetting unsaturated polyester resin waste according to claim 1, it is characterised in that institute
The modified monomer stated is acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, metering system
Acetoacetic ester, butyl acrylate, butyl methacrylate, Isooctyl acrylate monomer, vinyl acetate, long alkyl chain acrylate, third
One or more in alkene cyanogen and styrene.
3. the regenerating and modifying method of thermosetting unsaturated polyester resin waste according to claim 1, it is characterised in that with
Quality meter, the consumption of described modified monomer is the 5~200% of modified substrate quality.
4. the regenerating and modifying method of thermosetting unsaturated polyester resin waste according to claim 1, it is characterised in that institute
The quality for the catalyst stated is the 0.1~1.5% of modified substrate quality.
5. the regenerating and modifying method of thermosetting unsaturated polyester resin waste according to claim 1, it is characterised in that institute
The alcoholysis agent stated is the one or more in water, ethylene glycol and propane diols.
6. the regenerating and modifying method of the thermosetting unsaturated polyester resin waste according to any one of Claims 1 to 5, it is special
Levy and be, comprise the following steps：
(1) modified substrate, alcoholysis agent and catalyst are added in aqueous dispersions, using high-shear emulsifying point at 80~100 DEG C
It is casually arranged with the standby scattered 30~180min of progress shearing, catalytic activation modified substrate；
(2) aqueous dispersions, initiator and modified monomer are added into the slurry of the modified substrate after catalytic activation, 80~100
DEG C low suspension polymerization, cold filtration obtains modified heat convertible unsaturated polyester resin.
7. according to the regenerating and modifying method of thermosetting unsaturated polyester resin waste according to claim 6, its feature exists
In in step (1), the shearing scattered time is 30~60min.
8. according to the regenerating and modifying method of thermosetting unsaturated polyester resin waste according to claim 6, its feature exists
In in step (2), the filtrate of cold filtration is back to step (1) as aqueous dispersions.
9. the regenerating and modifying method of the thermosetting unsaturated polyester resin waste according to any one of Claims 1 to 5, it is special
Levy and be, comprise the following steps：
(I) modified substrate, alcoholysis agent, catalyst, emulsifying agent and modified monomer are added in aqueous dispersions, using high shear breast
Change dispersing apparatus and carry out the scattered 30~180min of shearing, obtain modified suspending emulsion；
(II) modified suspending emulsion is continuously added drop-wise in the aqueous solution containing emulsifying agent and initiator, it is newborn at 80~100 DEG C
Liquid polymerize, and cold filtration obtains modified heat convertible unsaturated polyester resin.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110551404A (en) * | 2019-07-06 | 2019-12-10 | 新三和石化(福建)股份公司 | Waste resin reclaimed material and preparation method thereof |
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