CN102453285A - Biodegradable polystyrene composition and preparation method thereof - Google Patents
Biodegradable polystyrene composition and preparation method thereof Download PDFInfo
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- CN102453285A CN102453285A CN201010517789XA CN201010517789A CN102453285A CN 102453285 A CN102453285 A CN 102453285A CN 201010517789X A CN201010517789X A CN 201010517789XA CN 201010517789 A CN201010517789 A CN 201010517789A CN 102453285 A CN102453285 A CN 102453285A
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Abstract
The invention provides a biodegradable polystyrene composition, which is characterized by containing polystyrene and a polymer of styrene and aliphatic-aromatic copolyester. The weight average molecular weight of the composition is 0.8*10<5> to 4.0*10<5>, the biodegradation rate of the composition is 10-30 weight percent according to ASTM D5338-92, the aliphatic-aromatic copolyester is biodegradable aliphatic-aromatic copolyester, and the content of the aliphatic-aromatic copolyester in the polymer of the styrene and the aliphatic-aromatic copolyester is 1-15 weight percent based on the total weight of the composition. The invention also provides a preparation method of the biodegradable polystyrene composition. While maintaining the mechanical properties of polystyrene, the polystyrene composition also has excellent biodegradable properties.
Description
Technical field
The present invention relates to a kind of biodegradable polyphenylacetylene combination and preparation method thereof.
Background technology
PS (PS) is because of it has that matter is hard, the transparency is good, rigidity, electrical insulating property, agent of low hygroscopicity, cheap, easy dyeing, be prone to processing, thermal conductivity not with characteristics such as temperature variation; Have application widely in industry and civilian every field, become one of current four big general-purpose plastics.Along with the continuous increase of polystyrene resin consumption, produced increasing PS waste product.Because the PS Stability Analysis of Structures is difficult to degraded under field conditions (factors), forms " white pollution " that ecotope is constituted a serious threat.How to handle " white garbage ", then become the focus of people's concern in recent years.
The method of handling deposed polystyrene at present is a lot, and traditional treatment process has burning method, landfill method, cyclic regeneration method.But because the singularity of PS character, the use of these traditional methods is restricted.Burning method can reclaim heat energy, but in combustion processes, produces a large amount of CO and CO
2Deng gas, thereby environment is caused secondary pollution; The PS chemical property is stable, be difficult for by microbiological degradation at occurring in nature, so landfill method can not fundamentally solve the pollution problem of waste; And the physicals of the polymkeric substance that obtains of reprocessing is far away from original copolymer, and cost that it is high and low excessively return rate let prestige and step back.
In recent years, effective processing of p-poly-phenyl ethene has all received the attention of height in countries in the world, carry out thermal destruction, catalyzed degradation and photodegradation etc. like p-poly-phenyl ethene, is considered to handle the effective means of deposed polystyrene.On PS Journal of Molecular Catalysis thermo-cracking system oil tech, obtained tangible progress like patent US 48516101, US 5078385, CN 1097431A and CN 1106371A; Patent CN1290920C discloses the preparation method of photodegradation nano composite plastics.But in heterogeneous catalyst heat scission reaction process, it is to be solved to exist many problems to have, like heat transfer, carbon distribution, catalyst regeneration and recovery problem; And aspect the photochemical catalysis cracking, then exist the deposed polystyrene incomplete problem of degrading.
Therefore, how to reduce the baneful influence of waste polystyrene, remain the major issue that needs to be resolved hurrily ecotope.
Summary of the invention
To the problems referred to above, contriver of the present invention looks for another way, and carries out modification through p-poly-phenyl ethene, makes it when keeping original mechanical property, also possess certain biodegradable ability.
The purpose of this invention is to provide a kind of biodegradable polyphenylacetylene combination and preparation method thereof.
Another object of the present invention provides a kind of biodegradable polyphenylacetylene combination that utilizes method for preparing.
Therefore aliphatic-aromatic copolyester, had both kept good thermotolerance of aromatic polyester and mechanical property to a certain extent owing to contain aromatic structure unit and aliphatic structure unit on the main chain, had had the biodegradable of aliphatic polyester again concurrently.
Contriver of the present invention finds under study for action; In vinylbenzene matrix, disperse biodegradable aliphatic-aromatic copolyester; Obtain containing the polyphenylacetylene combination of the polymkeric substance of PS and PS and aliphatic-aromatic copolyester, this polyphenylacetylene combination has certain biodegradable.
The invention provides a kind of biodegradable polyphenylacetylene combination, it is characterized in that, said compsn contains the polymkeric substance of PS and vinylbenzene and aliphatic-aromatic copolyester, and the weight-average molecular weight of said compsn is 0.8 * 10
5-4.0 * 10
5The biological degradation rate according to ASTM D5338-92 of said compsn is 10-30 weight %; Wherein, Said aliphatic-aromatic copolyester is biodegradable aliphatic-aromatic copolyester, is benchmark with the total amount of said compsn, and the content of aliphatic-aromatic copolyester part is 1-15 weight % in the polymkeric substance of said vinylbenzene and aliphatic-aromatic copolyester.
The present invention also provides a kind of preparation method of biodegradable polyphenylacetylene combination, it is characterized in that, this method is included under the radical polymerization condition; The solution of aliphatic-aromatic copolyester is contacted with styrene solution; After removing unreacted monomer and solvent, obtain biodegradable polyphenylacetylene combination, wherein; Said aliphatic-aromatic copolyester is biodegradable aliphatic-aromatic copolyester, and said polymeric condition makes that the weight-average molecular weight of compsn is 0.8 * 10
5-4.0 * 10
5The biological degradation rate according to ASTM D5338-92 of said compsn is 10-30 weight %; And the consumption of the solution of aliphatic-aromatic copolyester makes that the total amount with the said biodegradable polyphenylacetylene combination that obtains is a benchmark, and aliphatic-aromatic copolyester content partly is 1-15 weight % in the polymkeric substance of said vinylbenzene and aliphatic-aromatic copolyester.
The present invention also provides the biodegradable polyphenylacetylene combination by above-mentioned preparing method's preparation.
The polyphenylacetylene combination for preparing among the present invention is compared with PS; Has suitable even better mechanical property; Stretching yield stress like the polyphenylacetylene combination among the embodiment 1-3 is all slightly high than Comparative Examples 1; Owing to the existence of aliphatic-aromatic copolyester, said composition can be partly by biological degradation, like the polyphenylacetylene combination among the embodiment 3 simultaneously; When not changing its mechanical property, the biological degradation rate according to ASTM D5338-92 of this polyphenylacetylene combination (being 20 all compost rate of weight loss among the present invention) is up to 22.9 weight %.
Embodiment
The invention provides a kind of biodegradable polyphenylacetylene combination, it is characterized in that, said compsn contains the polymkeric substance of PS and vinylbenzene and aliphatic-aromatic copolyester, and the weight-average molecular weight of said compsn is 0.8 * 10
5-4.0 * 10
5, be preferably 1.0 * 10
5-3.0 * 10
5, further be preferably 1.1 * 10
5-2.0 * 10
5, most preferably be 1.3 * 10
5-1.7 * 10
5The biological degradation rate according to ASTMD5338-92 of said compsn is 10-30 weight %, further is preferably 15-25 weight %.
Wherein, Said aliphatic-aromatic copolyester is biodegradable aliphatic-aromatic copolyester; Total amount with said compsn is a benchmark; The content of aliphatic-aromatic copolyester part is 1-15 weight % in the polymkeric substance of said vinylbenzene and aliphatic-aromatic copolyester, preferably, is benchmark with the total amount of said compsn; The content of aliphatic-aromatic copolyester part is 2-10 weight % in the polymkeric substance of said vinylbenzene and aliphatic-aromatic copolyester, further is preferably 4-6 weight %.Through using biodegradable aliphatic-aromatic copolyester, can make compsn of the present invention have required biodegradable.Be controlled in the above-mentioned preferable range through the content that makes biodegradable aliphatic-aromatic copolyester, can make the mechanical property of compsn of the present invention and PS suitable, perhaps satisfy the request for utilization of PS use occasion.
According to the present invention; Said biodegradable aliphatic-aromatic copolyester can be to well known to a person skilled in the art various biodegradable aliphatic-aromatic copolyesters; As long as possess biodegradable; In order to make polyphenylacetylene combination possess better properties, under the preferable case, the weight-average molecular weight of said aliphatic-aromatic copolyester is 0.8 * 10
5-1.5 * 10
5, further be preferably 1.0 * 10
5-1.3 * 10
5, most preferably be 1.1 * 10
5-1.2 * 10
5
In the polyphenylacetylene combination of the present invention; The polymkeric substance of said vinylbenzene and aliphatic-aromatic copolyester is preferably the graftomer of vinylbenzene and aliphatic-aromatic copolyester; And percentage of grafting is preferably 3%-25%, further is preferably 5%-20%, most preferably is 8%-15%.Through infrared measurement compsn of the present invention, at 660cm
-1The place can observe in one strong peak, and what vinylbenzene and aliphatic-aromatic copolyester formation in the compsn be describeds is graftomer.Through control aliphatic-aromatic copolyester percentage of grafting in above-mentioned scope, can guarantee the mechanical property and the biodegradable of gained polyphenylacetylene combination better.Among the present invention, percentage of grafting is continued to use the conventional definition in this area, and percentage of grafting is a grafting efficiency, the total mass of the quality of percentage of grafting=graft copolymer/reaction resulting polymers.
Aliphatic-aromatic copolyester described in the present invention is a notion well known in the art; Promptly form by aromatic structure unit and aliphatic structure unit; Said aromatic structure unit derives from the binary aliphatic alcohol ester monomer of aromatic binary carboxylic acid; Said aliphatic structure unit derives from the binary aliphatic alcohol ester monomer of aliphatic dicarboxylic acid, and is benchmark with the monomeric total mole number of copolyesters, and the monomeric content of binary aliphatic alcohol ester of said aliphatic dicarboxylic acid is preferably greater than 40 moles of %; Further be preferably more than 50 moles of %, most preferably be greater than 60 moles of %.
According to the present invention, said aliphatic dicarboxylic acid can be the aliphatic dicarboxylic acid of 2-10 for carbonatoms, is preferably the aliphatic dicarboxylic acid that carbonatoms is 2-8; Said aromatic binary carboxylic acid can be the aromatic binary carboxylic acid of 8-14 for carbonatoms, is preferably the aromatic binary carboxylic acid that carbonatoms is 8-12; Said aliphatic dihydroxy alcohol can be the aliphatic dihydroxy alcohol of 2-10 for carbonatoms, is preferably the aliphatic dihydroxy alcohol that carbonatoms is 2-8.
According to the present invention; The aliphatic dicarboxylic acid, aromatic binary carboxylic acid and the aliphatic dihydroxy alcohol that meet above-mentioned requirements can have a variety of; Preferably; Said aliphatic dicarboxylic acid is a hexanodioic acid, and said aromatic binary carboxylic acid is a terephthalic acid, and said aliphatic dihydroxy alcohol is at least a in terepthaloyl moietie, Ucar 35, butyleneglycol and the pinakon.
Can have multiple by the formed aliphatic-aromatic copolyester of above-mentioned aliphatic dicarboxylic acid, aromatic binary carboxylic acid and aliphatic dihydroxy alcohol; Under the preferable case; Said aliphatic-aromatic copolyester is at least a in terephthalic acid terepthaloyl moietie-co-adipate glycol copolyesters (PETA), terephthaldehyde's acid propylene glycol-co-hexanodioic acid Ucar 35 copolyesters (PPTA), terephthalic acid butyleneglycol-co-hexanodioic acid butyleneglycol copolyesters (PBTA) and the terephthalic acid pinakon-co-hexanodioic acid pinakon copolyesters (PHTA); Further under the preferable case, said aliphatic-aromatic copolyester is terephthalic acid butyleneglycol-co-hexanodioic acid butyleneglycol copolyesters (PBTA) and terephthalic acid pinakon-co-hexanodioic acid pinakon copolyesters (PHTA).
In order to embody the characteristic of the biodegradable polyphenylacetylene combination of the present invention better; (total amount with simple mixtures is a benchmark to the simple mixtures of contriver's p-poly-phenyl ethene of the present invention, terephthalic acid butyleneglycol-co-hexanodioic acid butyleneglycol copolyesters (PBTA), PS and PBTA; The content of PBTA is 4.9 weight %) and the biodegradable of compsn P1 of the present invention test; The biological degradation rate of discovery is respectively 0,60 weight %, 1.8 weight % and 16.5 weight %; Wherein, The biodegradable test of the simple mixtures of said PS, PS and PBTA and P1 is 20 all compost rate of weight loss, and the biodegradable test of PBTA is 87 days compost rate of weight loss.Although the time of PBTA test is shorter; But the biological degradation rate up to 60 weight % is arranged still; And 20 all compost rate of weight loss of the simple mixtures of PBTA and PS are merely 1.8 weight %; Not only, also under similarity condition, test the biological degradation rate that obtains, simultaneously far below P1 among the present invention far below the biological degradation rate of PBTA; 20 of P1 all compost rate of weight loss also are lower than 87 days compost rate of weight loss of PBTA among the present invention; This shows that compsn provided by the invention is not the simple mixtures of PS and aliphatic-aromatic copolyester, vinylbenzene and aliphatic-aromatic copolyester have formed polymkeric substance; Thereby make the biological degradation rate according to ASTM D5338-92 of compsn of the present invention be superior to the simple mixtures of PS and PS and aliphatic-aromatic copolyester, but than the biological degradation rate variance of aliphatic-aromatic copolyester.
The invention provides a kind of preparation method of biodegradable polyphenylacetylene combination, it is characterized in that, this method is included under the radical polymerization condition; The solution of aliphatic-aromatic copolyester is contacted with styrene solution; After removing unreacted monomer and solvent, obtain biodegradable polyphenylacetylene combination, wherein; Said aliphatic-aromatic copolyester is biodegradable aliphatic-aromatic copolyester, and said polymeric condition makes that the weight-average molecular weight of compsn is 0.8 * 10
4-4.0 * 10
5, be preferably 1.0 * 10
5-3.0 * 10
5, further be preferably 1.1 * 10
5-2.0 * 10
5, most preferably be 1.3 * 10
5-1.7 * 10
5The biological degradation rate according to ASTM D5338-92 of said compsn is 10-30 weight %, further is preferably 15-25 weight %; And the consumption of the solution of aliphatic-aromatic copolyester makes that the total amount with the said biodegradable polyphenylacetylene combination that obtains is a benchmark; The content of aliphatic-aromatic copolyester part is 1-15 weight % in the polymkeric substance of said vinylbenzene and aliphatic-aromatic copolyester; Be preferably 2-10 weight %, further be preferably 4-6 weight %.
According to the present invention, styrene solution is carried out radical polymerization in the presence of aliphatic-aromatic copolyester solution be to make the gained polyphenylacetylene combination satisfy one of key of degradation property and mechanical property requirements simultaneously.The polyphenylacetylene combination that is obtained by this method carries out mixing the compsn that obtains with biodegradable aliphatic-aromatic copolyester again after the radical polymerization with vinylbenzene essential distinction is arranged with direct.
According to the present invention; In order to make the polyphenylacetylene combination that obtains possess better mechanical property and biodegradable, said aliphatic-aromatic copolyester and cinnamic weight ratio can be 1: 6-90 is preferably 1: 7-50; Further be preferably 1: 10-50; Most preferably be 1: 20-30, under above-mentioned optimum condition, the S compositions that obtains can possess good biodegradable when keeping the vinylbenzene mechanical property.
According to the present invention; Aliphatic-aromatic copolyester contacts with styrene solution with the form of solution; Wherein, the concentration of aliphatic-aromatic copolyester is preferably 10-40 weight % in the said aliphatic-aromatic copolyester solution, further is preferably 20-32 weight %; Cinnamic concentration is preferably 40-95 weight % in the said styrene solution, further is preferably 60-95 weight %, most preferably is 75-95 weight %.Concentration through making aliphatic-aromatic copolyester solution and styrene solution is in above-mentioned scope; The percentage of grafting that can make aliphatic-aromatic copolyester and cinnamic graft copolymer in the gained polyphenylacetylene combination is in the scope of 3%-25%; Under the optimum condition; Make said percentage of grafting in the scope of 5%-20%, most preferably under the condition, making said percentage of grafting is being in the scope of 8%-15%.
The solution of above-mentioned aliphatic-aromatic copolyester and the solvent in the styrene solution can like toluene, YLENE or ethylbenzene etc., be preferably ethylbenzene for the conventional various aromatic hydrocarbon solvents in this area.
According to the present invention; The preparation method of the solution of said aliphatic-aromatic copolyester comprises that all can make aliphatic-aromatic copolyester consoluet method in solvent, heating means for example, and the temperature of said heating means can the dissolved temperature for any aliphatic-aromatic copolyester that makes; Be preferably 90-120 ℃; Consider from the accessibility of experimental implementation, most preferably be 100 ℃, use the boiling water bath heating.The time of said heating dissolves fully with aliphatic-aromatic copolyester and is as the criterion, and normally, can be 1-4 hour, is preferably 2-3 hour among the present invention.
According to the present invention, the characteristic of said aliphatic-aromatic copolyester is described at preceding text, repeats no more at this.
According to the present invention, to the qualification especially of condition of said contact, can be the condition of the conventional mass polymerization in this area, preferably, the condition of said contact comprises that temperature is 100-170 ℃, the time is 5-10 hour.
In order to obtain possessing the polyphenylacetylene combination of better mechanical property and biodegradable; Under the preferable case; Said contact comprises fs, subordinate phase and the phase III of successively carrying out, and the condition of said fs comprises that temperature is 100 ℃-130 ℃, and the time is 3-5 hour; The condition of said subordinate phase comprises that temperature is 130 ℃-140 ℃, and the time is 1.5-2.5 hour; The condition of said phase III comprises that temperature is 140 ℃-170 ℃, and the time is 1-2 hour.
According to the present invention; For the temperature that the styrene solution and the solution of aliphatic-aromatic copolyester are contacted the most at the beginning just can be more than 100 ℃; Preferably styrene solution is joined in the polymerization reaction kettle earlier, and heat said polymerization reaction kettle, make its temperature remain on the temperature that is not less than 100 ℃.In order to prevent that vinylbenzene from this process autohemagglutination taking place; Under the preferable case; In heat-processed, promptly in polymerization reaction kettle, feeding rare gas element protects; Said rare gas element is the conventional rare gas element of field of olefin polymerisation, and at least a as in the neutral element gas in the nitrogen and the periodic table of elements is preferably nitrogen.
According to the present invention, the method for initiated polymerization can be the ordinary method of this area, causes like thermal initiation or initiator.Initiator can be selected from least a in Potassium Persulphate, Di Cumyl Peroxide 99, hydrogen phosphide cumene, Lucidol or the peroxide di-t-butyl, preferably uses hydrogen phosphide cumene.The consumption of initiator is the 0.1-2 weight % of vinylbenzene total amount in the styrene solution, further is preferably 0.1-0.5 weight %, most preferably is 0.1-0.2 weight %.The present invention preferably uses the mode of thermal initiation.
In addition, in above-mentioned polymerization system, can also add auxiliary agents more well known in the art, like protective agent, inhibitor; Concrete as, 2,2; 4-trimethylammonium-1,2-EEDQ polymer (RD), four [3-(3,5-di-t-butyl-4-hydroxyl) phenylpropionic acid] pentaerythritol ester (1010), three (2; The 4-di-t-butyl) phenyl phosphites (168), distearyl pentaerythritol diphosphite (618), N-cyclohexyl-N '-diphenyl-para-phenylene diamine (4010), 2,2 '-methylene-bis (4-methyl-6-tert butyl) phenol (2246), 3,5-di-tert-butyl-hydroxy phenyl propionic acid octadecanol ester (1076) etc.; In addition; Can also add some thermo-stabilizers, concrete as, Zinic stearas, lead stearate, cadmium stearate etc.
For the aliphatics aromatic copolyester is better contacted with vinylbenzene; The present invention preferably uses whisking appliance to stir; Said whisking appliance can be the conventional whisking appliance in this area; Like anchor stirrer, grid agitator, single helix agitator, double ribbon agitator, set square middle and upper part, bottom helix agitator, wherein ribbon can be single ribbon or two ribbon.The present invention preferentially selects set square middle and upper part, bottom ribbon combined type whisking appliance for use, and stir speed (S.S.) can be 100-180rpm/min, is preferably 120-140rpm/min, most preferably is 125-138rpm/min.
According to the present invention; The said method that removes unreacted monomer and solvent can be the conventional method in this area; The present invention is preferably in devolatilizer, and under the vacuum state, the method through flash distillation removes unreacted monomer and solvent; The temperature of said flash distillation can be 180-210 ℃, further is preferably 185-195 ℃.
According to following examples content of the present invention is done further explanation.Carry out various performance tests through following method to preparing polyphenylacetylene combination.
1, weight-average molecular weight: according to gel permeation chromatography (gel chromatograph is the PL-GPC 220 type gel chromatographs of Britain PL company, is solvent with THF (THF), with the calibration of vinylbenzene standard specimen);
2, percentage of grafting: take by weighing the biodegradable polyphenylacetylene combination of certain mass, contact with 1: 50 weight ratio and acetone-butanone mixed solvent (wherein, acetone is 1: 1 with the volume ratio of butanone); After stirring, leave standstill 24h, on supercentrifuge with the centrifugal 30min of the speed of 4000r/min; Separate obtaining lower sediment, lower sediment is washed with above-mentioned mixed solvent, then centrifugal 10min under the speed of 4000r/min; Washing is-centrifugal three times altogether; The throw out that obtains is at last dried in baking oven to constant weight, the sedimentary weight of weighing, the percentage of grafting of sample is weight * 100% of the sedimentary weight/polyphenylacetylene combination of gained.
3, socle girder notched Izod impact strength: the method according to GB/T1843-2008 is tested
4, stretching yield stress: the method according to GB/T1040.2-2006 is tested
5, biodegradability test: the method according to ASTM D5338-92 is tested, and promptly compost buries the sheet method, and sample is pressed into 20mm * 20mm, the thick film of (0.2 ± 0.02) mm; Imbed in the compost after weighing; Put into thermostat container, temperature is (55 ± 2) ℃, and humidity is (65 ± 5) %.20 weeks back taking-up specimen is weighed after the clean dry.Characterize the biodegradable of sample with rate of weight loss.
Embodiment 1
(weight-average molecular weight is 1.1 * 10 with 72g terephthalic acid butyleneglycol-co-hexanodioic acid butyleneglycol copolyesters (PBTA)
5, aliphatics content is 75 moles of %, biological degradation rate is 60% (87 days compost), available from BASF AG) join in the 200g ethylbenzene, in boiling water bath, heat, stir and PBTA was dissolved fully in 2 hours.
With nitrogen air in the still is replaced fully; 1700g styrene monomer (Yanshan Petrochemical production) and 100g ethylbenzene are added in the still, add 1.8g protective agent 1076.Initiating method adopts thermal initiation.Polymeric kettle heats up under the 138rpm/min stir speed (S.S.), and said whisking appliance is set square middle and upper part, a bottom ribbon combined type whisking appliance; When the question response temperature reaches 100 ℃, under protection of nitrogen gas, the ethylbenzene solution of consoluet PBTA is added in the reaction kettle, continue to heat up.120 ℃ of following polymerizations 4 hours, 130 ℃ of following polymerizations 2 hours, 157 ℃ of following polymerizations 1.5 hours.After treating that polymerization is accomplished, the thickness body of polymerization gained is put into 185 ℃ devolatilizer, rapid flash distillation under vacuum state removes unreacted styrene monomer and solvent ethylbenzene.Obtain 1480g polyphenylacetylene combination P1, wherein, the content of PBTA is 4.9 weight %.Calculating the transformation efficiency of styrene monomer, is 82.8%.The compsn weight-average molecular weight is 1.4 * 10
5, the percentage of grafting of PBTA is 11.5%.P1 is carried out Mechanics Performance Testing and biodegradation test, and the result lists in the table 1.
Comparative Examples 1
Method according to embodiment 1 prepares polymkeric substance, and different is, does not add PBTA, obtains 1400g polymerisate DP1, and cinnamic transformation efficiency is 82.3%.The compsn weight-average molecular weight is 1.25 * 10
5DP1 is carried out Mechanics Performance Testing and biodegradation test, and the result lists in the table 1.
Comparative Examples 2
The polymer product DP1 that 95.1 weight part Comparative Examples 1 are obtained mixes with embodiment 1 identical PBTA with 4.9 weight parts source, obtains polystyrene blends DP2.The compsn weight-average molecular weight is 1.25 * 10
5, the percentage of grafting of PBTA is 0.DP2 is carried out Mechanics Performance Testing and biodegradation test, and the result lists in the table 1.
Comparative Examples 3
Method according to embodiment 1 prepares polyphenylacetylene combination, and different is, 260 gram PBTA are joined in the 200 gram ethylbenzenes, obtains 1620g polymerisate DP3, and wherein, the content of PBTA is 16 weight %, and cinnamic transformation efficiency is 80%.The compsn weight-average molecular weight is 1.6 * 10
5, the percentage of grafting of PBTA is 36%.DP3 is carried out Mechanics Performance Testing and biodegradation test, and the result lists in the table 1.
Comparative Examples 4
Method according to embodiment 1 prepares polyphenylacetylene combination; Different is, it is in 100 ℃ the 1700g vinylbenzene and 300g ethylbenzene that 72 gram PBTA solids are directly joined temperature, carries out polyreaction then; Obtain 1460g polymerisate DP4; Wherein, the content of PBTA is 4.9 weight %, and cinnamic transformation efficiency is 81.6%.The compsn weight-average molecular weight is 1.25 * 10
5, the percentage of grafting of PBTA is 0.DP4 is carried out Mechanics Performance Testing and biodegradation test, and the result lists in the table 1.
Embodiment 2
The PBTA of 60g is added in the 200g ethylbenzene, in boiling water bath, heat, stir and PBTA was dissolved fully in 2 hours.
With nitrogen air in the still is replaced fully; 1700g styrene monomer (Yanshan Petrochemical production) and 500g ethylbenzene are added in the still, add 1.8g protective agent 2246.Add the initiation reaction of 2g hydrogen phosphide cumene.Polymeric kettle heats up under the 125rpm/min stir speed (S.S.), and said whisking appliance is set square middle and upper part, a bottom ribbon combined type whisking appliance; When the question response temperature reaches 100 ℃, under protection of nitrogen gas, the ethylbenzene solution of consoluet PBTA is added in the reaction kettle, continue to heat up.105 ℃ of following polymerizations 5 hours, 135 ℃ of following polymerizations 2.5 hours, 140 ℃ of following polymerizations 2 hours.After treating that polymerization is accomplished, the thickness body of polymerization gained is discharged, put into 195 ℃ devolatilizer, rapid flash distillation under vacuum state removes unreacted styrene monomer and solvent ethylbenzene.Obtain 1420g polyphenylacetylene combination P2, wherein, the content of aliphatics aromatic copolyester is 4.2 weight %.Calculating the transformation efficiency of styrene monomer, is 80%.The compsn weight-average molecular weight is 1.3 * 10
5, the percentage of grafting of aliphatics aromatic copolyester is 9.1%.P2 is carried out Mechanics Performance Testing and biodegradation test, and the result lists in the table 1.
Embodiment 3
(PHTA, available from BASF AG, weight-average molecular weight is 1.2 * 10 with terephthalic acid pinakon-co-hexanodioic acid pinakon copolyesters of 85g
5, aliphatics content is 85 moles of %) add in the 200g ethylbenzene, in boiling water bath, heat, stir and PHTA was dissolved fully in 3 hours.
With nitrogen air in the still is replaced fully; 1700g styrene monomer (Yanshan Petrochemical production) and 300g ethylbenzene are added in the still.Initiating method adopts thermal initiation.Polymeric kettle heats up under the 130rpm/min stir speed (S.S.), and said whisking appliance is set square middle and upper part, a bottom ribbon combined type whisking appliance; When the question response temperature reaches 100 ℃, under protection of nitrogen gas, the ethylbenzene solution of consoluet PHTA is added in the reaction kettle, continue to heat up.At 130 ℃ of following polyase 13s hour, 140 ℃ of following polymerizations 1.5 hours, 170 ℃ of following polymerizations 1 hour.After treating that polymerization is accomplished, the thickness body of polymerization gained is put into 190 ℃ devolatilizer, rapid flash distillation under vacuum state removes unreacted styrene monomer and solvent ethylbenzene.Obtain 1520g polyphenylacetylene combination P3, wherein, the content of aliphatics aromatic copolyester is 5.6 weight %.Calculating the transformation efficiency of styrene monomer, is 84.2%.The compsn weight-average molecular weight is 1.65 * 10
5, the percentage of grafting of aliphatics aromatic copolyester is 14.3%.P3 is carried out Mechanics Performance Testing and biodegradation test, and the result lists in the table 1.
Embodiment 4
Method according to embodiment 1 prepares polyphenylacetylene combination, and different is, 49 gram PBTA are joined in the 200 gram ethylbenzenes, obtains 1460g polymerisate P4, and the content of PBTA is 3.1 weight %, and cinnamic transformation efficiency is 83%.The compsn weight-average molecular weight is 1.2 * 10
5, the percentage of grafting of PBTA is 3.8%.P4 is carried out Mechanics Performance Testing and biodegradation test, and the result lists in the table 1.
Embodiment 5
Method according to embodiment 1 prepares polyphenylacetylene combination, and different is, 108 gram PBTA are joined in the 200 gram ethylbenzenes, obtains 1490g polymerisate P5, and the content of PBTA is 7.2 weight %, and cinnamic transformation efficiency is 81.3%.The compsn weight-average molecular weight is 1.15 * 10
5, the percentage of grafting of PBTA is 14.8%.P5 is carried out Mechanics Performance Testing and biodegradation test, and the result lists in the table 1.
Embodiment 6
Method according to embodiment 1 prepares polyphenylacetylene combination, and different is, the speed that stirs in the polymerization process is 70rpm/ minute, obtains 1460g polymerisate P6, and the content of PBTA is 4.9 weight %, and cinnamic transformation efficiency is 81.6%.The compsn weight-average molecular weight is 1.2 * 10
5, the percentage of grafting of PBTA is 4.5%.P6 is carried out Mechanics Performance Testing and biodegradation test, and the result lists in the table 1.
Embodiment 7
Method according to embodiment 1 prepares polyphenylacetylene combination, and different is that terepthaloyl moietie-(PETA, available from BASF AG, weight-average molecular weight is 1.1 * 10 to co-adipic acid terepthaloyl moietie copolyesters to add the 72g terephthalic acid
5, aliphatics content is 65 moles of %) and replacement 72gPBTA.Obtain 1420 gram polymerisate P7, wherein, the content of PETA is 5.1 weight %, and the weight-average molecular weight of P7 is 1.3 * 10
5, the percentage of grafting of aliphatics aromatic copolyester is 10.5%.P7 is carried out Mechanics Performance Testing and biodegradation test, and the result lists in the table 1.
Table 1
By in the table 1 the result can find out; Obtain the PS that DP1 is homopolymerization in the Comparative Examples 1; DP1 does not possess any degradation capability under test condition; And the result of embodiment 1-3 shows, polyphenylacetylene combination of the present invention has also possessed considerable biodegradable on the basis that has kept the good mechanical performance.
Comparative Examples 2 is the mixture of PS and PBTA; 20 all compost rate of weight loss of the mixture that makes in the Comparative Examples 2 are merely 1.8 weight %; Comparing with embodiment 1 has very big gap; Only explain and to realize the present invention through simple mixing; The polyphenylacetylene combination that obtains in the embodiment of the invention 1 be through with styrene-grafted to aliphatic-aromatic copolyester, and control reaction is under these conditions, has just realized on the basis that keeps PS good mechanical performance, obtaining good biodegradability like this.
The content of PBTA is not within scope of the present invention in the Comparative Examples 3; Though the biodegradability of the polyphenylacetylene combination that obtains in the Comparative Examples 3 is fine; But simultaneously; The socle girder notched Izod impact strength also descends rapidly, and the polyphenylacetylene combination that makes does not so possess the good mechanical performance, greatly reduces the applicability of this polyphenylacetylene combination.
PBTA in the Comparative Examples 4 directly carries out polyreaction with solid form and vinylbenzene; Can find out from table 1; 20 all compost rate of weight loss of this polyphenylacetylene combination are merely 2.2 weight %, this explanation, and PBTA reacts with the form of solution and vinylbenzene could realize the present invention.
Compare with embodiment 1, the PBTA content of polymerisate P4 lower slightly than embodiment 1 among the embodiment 4, its good mechanical properties, but 20 all compost rate of weight loss are reduced to 5.4 weight % rapidly; The PBTA content of the polymerisate P5 of embodiment 5 is higher than the summary of embodiment 1, and 20 all compost rate of weight loss of P5 reach 24.6 weight %, but its socle girder notched Izod impact strength but drops to 0.85KJ/m
2, hence one can see that, has only the aliphatic-aromatic copolyester that uses proper content can be implemented on the basis that keeps the good mechanical performance, possesses considerable biodegradable simultaneously.
Claims (24)
1. a biodegradable polyphenylacetylene combination is characterized in that, said compsn contains the polymkeric substance of PS and vinylbenzene and aliphatic-aromatic copolyester, and the weight-average molecular weight of said compsn is 0.8 * 10
5-4.0 * 10
5The biological degradation rate according to ASTM D5338-92 of said compsn is 10-30 weight %; Wherein, Said aliphatic-aromatic copolyester is biodegradable aliphatic-aromatic copolyester, is benchmark with the total amount of said compsn, and the content of aliphatic-aromatic copolyester part is 1-15 weight % in the polymkeric substance of said vinylbenzene and aliphatic-aromatic copolyester.
2. compsn according to claim 1, wherein, the weight-average molecular weight of said compsn is 1.0 * 10
5-3.0 * 10
5, the biological degradation rate according to ASTM D5338-92 of said compsn is 15-25 weight %.
3. compsn according to claim 1 wherein, is a benchmark with the total amount of said compsn, and the content of aliphatic-aromatic copolyester part is 2-10 weight % in the polymkeric substance of said vinylbenzene and aliphatic-aromatic copolyester.
4. compsn according to claim 1, wherein, the weight-average molecular weight of said aliphatic-aromatic copolyester is 0.8 * 10
5-1.5 * 10
5
5. according to any described compsn among the claim 1-4, wherein, the polymkeric substance of said vinylbenzene and aliphatic-aromatic copolyester is the graftomer of vinylbenzene and aliphatic-aromatic copolyester, and percentage of grafting is 3%-20%.
6. according to any described compsn among the claim 1-4; Wherein, Said aliphatic-aromatic copolyester is made up of aromatic structure unit and aliphatic structure unit; Said aromatic structure unit derives from the binary aliphatic alcohol ester monomer of aromatic binary carboxylic acid; Said aliphatic structure unit derives from the binary aliphatic alcohol ester monomer of aliphatic dicarboxylic acid, and is benchmark with the monomeric total mole number of copolyesters, and the monomeric content of binary aliphatic alcohol ester of said aliphatic dicarboxylic acid is greater than 40 moles of %.
7. compsn according to claim 6; Wherein, Said aliphatic dicarboxylic acid is that carbonatoms is the aliphatic dicarboxylic acid of 2-10; Said aromatic binary carboxylic acid is that carbonatoms is the aromatic binary carboxylic acid of 8-14, and said aliphatic dihydroxy alcohol is that carbonatoms is the aliphatic dihydroxy alcohol of 2-10.
8. compsn according to claim 7, wherein, said aliphatic dicarboxylic acid is a hexanodioic acid, and said aromatic binary carboxylic acid is a terephthalic acid, and said aliphatic dihydroxy alcohol is at least a in terepthaloyl moietie, Ucar 35, butyleneglycol and the pinakon.
9. compsn according to claim 8; Wherein, said aliphatic-aromatic copolyester is selected from least a in terephthalic acid terepthaloyl moietie-co-adipate glycol copolyesters, terephthaldehyde's acid propylene glycol-co-hexanodioic acid Ucar 35 copolyesters, terephthalic acid butyleneglycol-co-hexanodioic acid butyleneglycol copolyesters and the terephthalic acid pinakon-co-hexanodioic acid pinakon copolyesters.
10. the preparation method of a biodegradable polyphenylacetylene combination is characterized in that, this method is included under the radical polymerization condition; The solution of aliphatic-aromatic copolyester is contacted with styrene solution; After removing unreacted monomer and solvent, obtain biodegradable polyphenylacetylene combination, wherein; Said aliphatic-aromatic copolyester is biodegradable aliphatic-aromatic copolyester, and said polymeric condition makes that the weight-average molecular weight of compsn is 0.8 * 10
5-4.0 * 10
5The biological degradation rate according to ASTM D5338-92 of said compsn is 10-30 weight %; And the consumption of the solution of aliphatic-aromatic copolyester makes that the total amount with the said biodegradable polyphenylacetylene combination that obtains is a benchmark, and aliphatic-aromatic copolyester content partly is 1-15 weight % in the polymkeric substance of said vinylbenzene and aliphatic-aromatic copolyester.
11. method according to claim 10, wherein, said polymeric condition makes that the weight-average molecular weight of compsn is 1.0 * 10
5-3.0 * 10
5The biological degradation rate according to ASTM D5338-92 of said compsn is 15-25 weight %; And the consumption of the solution of aliphatic-aromatic copolyester makes that the total amount with the said biodegradable polyphenylacetylene combination that obtains is a benchmark, and aliphatic-aromatic copolyester content partly is 2-10 weight % in the polymkeric substance of said vinylbenzene and aliphatic-aromatic copolyester.
12. method according to claim 10, wherein, the cinnamic weight ratio in aliphatic-aromatic copolyester in the solution of said aliphatic-aromatic copolyester and the styrene solution is 1: 6-90.
13. method according to claim 12, wherein, the cinnamic weight ratio in aliphatic-aromatic copolyester in the solution of said aliphatic-aromatic copolyester and the styrene solution is 1: 7-50.
14. method according to claim 10, wherein, cinnamic concentration is 40-95 weight % in the said styrene solution.
15. method according to claim 10, wherein, the concentration of aliphatic-aromatic copolyester is 10-40 weight % in the said aliphatic-aromatic copolyester solution.
16. method according to claim 10, wherein, the weight-average molecular weight of said aliphatic-aromatic copolyester is 0.8 * 10
5-1.5 * 10
5
17. according to any described method among the claim 10-16; Wherein, Said aliphatic-aromatic copolyester is made up of aromatic structure unit and aliphatic structure unit; Said aromatic structure unit derives from the binary aliphatic alcohol ester monomer of aromatic binary carboxylic acid; Said aliphatic structure unit derives from the binary aliphatic alcohol ester monomer of aliphatic dicarboxylic acid, and is benchmark with the monomeric total mole number of copolyesters, and the monomeric content of binary aliphatic alcohol ester of said aliphatic dicarboxylic acid is greater than 40 moles of %.
18. method according to claim 17; Wherein, Said aliphatic dicarboxylic acid is that carbonatoms is the aliphatic dicarboxylic acid of 2-10; Said aromatic binary carboxylic acid is that carbonatoms is the aromatic binary carboxylic acid of 8-14, and said aliphatic dihydroxy alcohol is that carbonatoms is the aliphatic dihydroxy alcohol of 2-10.
19. method according to claim 18, wherein, said aliphatic dicarboxylic acid is a hexanodioic acid, and said aromatic binary carboxylic acid is a terephthalic acid, and said aliphatic dihydroxy alcohol is at least a in terepthaloyl moietie, Ucar 35, butyleneglycol and the pinakon.
20. method according to claim 19; Wherein, said aliphatic-aromatic copolyester is selected from least a in terephthalic acid terepthaloyl moietie-co-adipate glycol copolyesters, terephthaldehyde's acid propylene glycol-co-hexanodioic acid Ucar 35 copolyesters, terephthalic acid butyleneglycol-co-hexanodioic acid butyleneglycol copolyesters and the terephthalic acid pinakon-co-hexanodioic acid pinakon copolyesters.
21. according to any described method among the claim 10-16, wherein, the condition of said contact comprises, under agitation carries out, temperature is 100-170 ℃, and the time is 5-10 hour.
22. method according to claim 21, wherein, said contact comprises fs, subordinate phase and phase III, and the condition of said fs comprises that temperature is 100 ℃-130 ℃, and the time is 3-5 hour; The condition of said subordinate phase comprises that temperature is 130 ℃-140 ℃, and the time is 1.5-2.5 hour; The condition of said phase III comprises that temperature is 140 ℃-170 ℃, and the time is 1-2 hour.
23. according to claim 21 or 22 described methods, wherein, the speed of said stirring is 100-180rpm/ minute.
24. biodegradable polyphenylacetylene combination by any described method preparation among the claim 10-23.
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