CN102453285B - Biodegradable polystyrene composition and preparation method thereof - Google Patents
Biodegradable polystyrene composition and preparation method thereof Download PDFInfo
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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 polystyrene composition and preparation method thereof.
Background technology
Polystyrene (PS) is because it has that matter is hard, the transparency is good, rigidity, electrical insulating property, agent of low hygroscopicity, cheap, easy dyeing, easily processing, thermal conductivity such as do not vary with temperature at the characteristics, have application widely in industry and civilian every field, become one of current four large general-purpose plastics.Along with the continuous increase of polystyrene resin consumption, produced increasing polystyrene waste product.Due to the polystyrene Stability Analysis of Structures, hard degradation, form " white pollution " that ecotope is constituted a serious threat under field conditions (factors).How to process " white garbage ", become the focus of people's concern in recent years.
The method of processing at present deposed polystyrene is a lot, and traditional treatment process has burning method, landfill method, cyclic regeneration method.But due to the singularity of polystyrene character, the use of these traditional methods is restricted.Burning method can reclaim heat energy, but produces a large amount of CO and CO in combustion processes
2Deng gas, thereby environment is caused secondary pollution; The polystyrene stable chemical nature be difficult for being decomposed by microorganism 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 the cost that it is high and too low return rate allow prestige and step back.
In recent years, effective processing of p-poly-phenyl ethene all has been subject to the attention of height in countries in the world, carry out thermal destruction, catalyzed degradation and photodegradation etc. as p-poly-phenyl ethene, is considered to process the effective means of deposed polystyrene.As patent US 48516101, US 5078385, CN 1097431A and CN 1106371A technical the making significant progress of polystyrene Journal of Molecular Catalysis thermo-cracking liquefaction; Patent CN1290920C discloses the preparation method of light degradable nano composite plastics.But in heterogeneous catalyst heat scission reaction process, exist many problems to have to be solved, as heat transfer, carbon distribution, catalyst regeneration and recovery problem; And aspect photocatalytic cleavage, exist the incomplete problem of deposed polystyrene degraded.
Therefore, how to reduce waste polystyrene to the baneful influence of ecotope, remain the major issue that needs to be resolved hurrily.
Summary of the invention
For the problems referred to above, the present inventor looks for another way, and carries out modification by p-poly-phenyl ethene, makes it also possess certain biodegradable ability when keeping original mechanical property.
The purpose of this invention is to provide a kind of Biodegradable polystyrene composition and preparation method thereof.
Another object of the present invention is to provide a kind of Biodegradable polystyrene composition that utilizes the aforesaid method preparation.
Therefore aliphatic-aromatic copolyester, had both kept the good thermotolerance of aromatic polyester and mechanical property to a certain extent owing to containing aromatic structure unit and aliphatic structure unit on main chain, had had again the biodegradable of aliphatic polyester concurrently.
The present inventor finds under study for action, disperse biodegradable aliphatic-aromatic copolyester in vinylbenzene matrix, obtain containing the polyphenylacetylene combination of the polymkeric substance of polystyrene and polystyrene and aliphatic-aromatic copolyester, this polyphenylacetylene combination has certain biodegradable.
The invention provides a kind of Biodegradable polystyrene composition, it is characterized in that, described composition contains the polymkeric substance of polystyrene and vinylbenzene and aliphatic-aromatic copolyester, and the weight-average molecular weight of described composition is 0.8 * 10
5-4.0 * 10
5The biological degradation rate according to ASTM D5338-92 of described composition is the 10-30 % by weight, wherein, described aliphatic-aromatic copolyester is biodegradable aliphatic-aromatic copolyester, take the total amount of described composition as benchmark, in the polymkeric substance of described vinylbenzene and aliphatic-aromatic copolyester, the content of aliphatic-aromatic copolyester part is the 1-15 % by weight.
The present invention also provides a kind of preparation method of Biodegradable polystyrene composition, it is characterized in that, the 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 polystyrene composition, wherein, described aliphatic-aromatic copolyester is biodegradable aliphatic-aromatic copolyester, and it is 0.8 * 10 that the condition of described polymerization makes the weight-average molecular weight of composition
5-4.0 * 10
5The biological degradation rate according to ASTM D5338-92 of described composition is the 10-30 % by weight, and the total amount of the described Biodegradable polystyrene composition that the consumption of the solution of aliphatic-aromatic copolyester makes to obtain is benchmark, and in the polymkeric substance of described vinylbenzene and aliphatic-aromatic copolyester, the content of aliphatic-aromatic copolyester part is the 1-15 % by weight.
The present invention also provides the Biodegradable polystyrene composition by above-mentioned preparation method's preparation.
The polyphenylacetylene combination for preparing in the present invention is compared with polystyrene, has quite even better mechanical property, stretching yield stress as the polyphenylacetylene combination in embodiment 1-3 is all slightly high than Comparative Examples 1, while is due to the existence of aliphatic-aromatic copolyester, said composition can partly be biodegradable, as the polyphenylacetylene combination in embodiment 3, 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 in the present invention) is up to 22.9 % by weight.
Embodiment
The invention provides a kind of Biodegradable polystyrene composition, it is characterized in that, described composition contains the polymkeric substance of polystyrene and vinylbenzene and aliphatic-aromatic copolyester, and the weight-average molecular weight of described composition is 0.8 * 10
5-4.0 * 10
5, be preferably 1.0 * 10
5-3.0 * 10
5, more 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 described composition is the 10-30 % by weight, more preferably the 15-25 % by weight.
Wherein, described aliphatic-aromatic copolyester is biodegradable aliphatic-aromatic copolyester, take the total amount of described composition as benchmark, in the polymkeric substance of described vinylbenzene and aliphatic-aromatic copolyester, the content of aliphatic-aromatic copolyester part is the 1-15 % by weight, preferably, take the total amount of described composition as benchmark, in the polymkeric substance of described vinylbenzene and aliphatic-aromatic copolyester, the content of aliphatic-aromatic copolyester part is the 2-10 % by weight, more preferably the 4-6 % by weight.By using biodegradable aliphatic-aromatic copolyester, can make composition of the present invention have required biodegradable.Be controlled in above-mentioned preferable range by the content that makes biodegradable aliphatic-aromatic copolyester, can make the mechanical property of composition of the present invention and polystyrene suitable, perhaps satisfy the service requirements of polystyrene use occasion.
According to the present invention, described 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 preferable case, the weight-average molecular weight of described aliphatic-aromatic copolyester is 0.8 * 10
5-1.5 * 10
5, more preferably 1.0 * 10
5-1.3 * 10
5, most preferably be 1.1 * 10
5-1.2 * 10
5
In polyphenylacetylene combination of the present invention, the polymkeric substance of described vinylbenzene and aliphatic-aromatic copolyester is preferably the graftomer of vinylbenzene and aliphatic-aromatic copolyester, and percentage of grafting is preferably 3%-25%, and more preferably 5%-20%, most preferably be 8%-15%.By infrared measurement composition of the present invention, at 660cm
-1The place can observe in one strong peak, and what vinylbenzene in composition and aliphatic-aromatic copolyester formation be describeds is graftomer.Percentage of grafting by controlling aliphatic-aromatic copolyester can guarantee mechanical property and the biodegradable of gained polyphenylacetylene combination better in above-mentioned scope.In the present invention, percentage of grafting is continued to use the definition of this area routine, and percentage of grafting is 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 concept well known in the art, namely formed by aromatic structure unit and aliphatic structure unit, described aromatic structure unit derives from the binary aliphatic alcohol ester monomer of aromatic binary carboxylic acid, described aliphatic structure unit derives from the binary aliphatic alcohol ester monomer of aliphatic dicarboxylic acid, and take the total mole number of the monomer of copolyesters as benchmark, the content of the binary aliphatic alcohol ester monomer of described aliphatic dicarboxylic acid is preferably greater than 40 % by mole, more preferably greater than 50 % by mole, most preferably be greater than 60 % by mole.
According to the present invention, described 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; Described 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; Described 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, described aliphatic dicarboxylic acid is hexanodioic acid, described aromatic binary carboxylic acid is terephthalic acid, and described aliphatic dihydroxy alcohol is at least a in ethylene glycol, propylene glycol, butyleneglycol and hexylene glycol.
by above-mentioned aliphatic dicarboxylic acid, the formed aliphatic-aromatic copolyester of aromatic binary carboxylic acid and aliphatic dihydroxy alcohol can have multiple, under preferable case, described aliphatic-aromatic copolyester is terephthalate-co-adipate glycol copolyesters (PETA), terephthaldehyde's acid propylene glycol-co-hexanodioic acid propanediol copolyester (PPTA), at least a in terephthalic acid butyleneglycol-co-hexanodioic acid butanediol copolyester (PBTA) and terephthalic acid hexylene glycol-co-hexanodioic acid hexylene glycol copolyesters (PHTA), further under preferable case, described aliphatic-aromatic copolyester is terephthalic acid butyleneglycol-co-hexanodioic acid butanediol copolyester (PBTA) and terephthalic acid hexylene glycol-co-hexanodioic acid hexylene glycol copolyesters (PHTA).
in order to embody better the feature of Biodegradable polystyrene composition of the present invention, the present inventor's p-poly-phenyl ethene, terephthalic acid butyleneglycol-co-hexanodioic acid butanediol copolyester (PBTA), the simple mixtures of polystyrene and PBTA is (take the total amount of simple mixtures as benchmark, the content of PBTA is 4.9 % by weight) and the biodegradable of composition P1 of the present invention test, the biological degradation rate of discovery is respectively 0, 60 % by weight, 1.8 % by weight and 16.5 % by weight, wherein, described polystyrene, the biodegradable test of the simple mixtures of polystyrene 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 % by weight is arranged still, and 20 all compost rate of weight loss of the simple mixtures of PBTA and polystyrene are only 1.8 % by weight, not only far below the biological degradation rate of PBTA, also test the biological degradation rate that obtains under similarity condition far below P1 in the present invention, simultaneously, in the present invention, 20 of P1 all compost rate of weight loss are also lower than 87 days compost rate of weight loss of PBTA, this shows, composition provided by the invention is not the simple mixtures of polystyrene and aliphatic-aromatic copolyester, vinylbenzene and aliphatic-aromatic copolyester have formed polymkeric substance, thereby the biological degradation rate according to ASTM D5338-92 that makes composition of the present invention is better than the simple mixtures of polystyrene and polystyrene and aliphatic-aromatic copolyester, but the biological degradation rate variance than aliphatic-aromatic copolyester.
The invention provides a kind of preparation method of Biodegradable polystyrene composition, it is characterized in that, the 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 polystyrene composition, wherein, described aliphatic-aromatic copolyester is biodegradable aliphatic-aromatic copolyester, and it is 0.8 * 10 that the condition of described polymerization makes the weight-average molecular weight of composition
4-4.0 * 10
5, be preferably 1.0 * 10
5-3.0 * 10
5, more 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 described composition is the 10-30 % by weight, more preferably the 15-25 % by weight; And the total amount of the described Biodegradable polystyrene composition that the consumption of the solution of aliphatic-aromatic copolyester makes to obtain is benchmark, in the polymkeric substance of described vinylbenzene and aliphatic-aromatic copolyester, the content of aliphatic-aromatic copolyester part is the 1-15 % by weight, be preferably the 2-10 % by weight, more preferably the 4-6 % by weight.
According to the present invention, styrene solution is carried out radical polymerization under aliphatic-aromatic copolyester solution exists be to make the gained polyphenylacetylene combination satisfy simultaneously one of key of degradation property and mechanical property requirements.The polyphenylacetylene combination that is obtained by the method has essential distinction with the composition that directly vinylbenzene is carried out after radical polymerization again being mixed to get with biodegradable aliphatic-aromatic copolyester.
According to the present invention, in order to make the polyphenylacetylene combination that obtains possess better mechanical property and biodegradable, described aliphatic-aromatic copolyester and cinnamic weight ratio can be 1: 6-90, be preferably 1: 7-50, more 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, in described aliphatic-aromatic copolyester solution, the concentration of aliphatic-aromatic copolyester is preferably the 10-40 % by weight, more preferably the 20-32 % by weight; In described styrene solution, cinnamic concentration is preferably the 40-95 % by weight, and more preferably the 60-95 % by weight, most preferably be the 75-95 % by weight.Concentration by making aliphatic-aromatic copolyester solution and styrene solution is in above-mentioned scope, can make the percentage of grafting of aliphatic-aromatic copolyester and cinnamic graft copolymer in the gained polyphenylacetylene combination in the scope of 3%-25%, under optimum condition, make described percentage of grafting in the scope of 5%-20%, most preferably under condition, making described percentage of grafting is being in the scope of 8%-15%.
The solution of above-mentioned aliphatic-aromatic copolyester and the solvent in styrene solution can for the various aromatic hydrocarbon solvents of this area routine, as toluene, dimethylbenzene or ethylbenzene etc., be preferably ethylbenzene.
According to the present invention, the preparation method of the solution of described aliphatic-aromatic copolyester comprises that all can make aliphatic-aromatic copolyester consoluet method in solvent, heating means for example, the temperature of described heating means can be any temperature that aliphatic-aromatic copolyester can be dissolved, be preferably 90-120 ℃, consider from the accessibility of experimental implementation, most preferably be 100 ℃, use the boiling water bath heating.The time of described heating dissolves fully with aliphatic-aromatic copolyester and is as the criterion, and normally, can be 1-4 hour, is preferably 2-3 hour in the present invention.
According to the present invention, the feature of described aliphatic-aromatic copolyester above describing, does not repeat them here.
According to the present invention, the condition of described contact is not particularly limited, can be the condition of the mass polymerization of this area routine, preferably, the condition of described 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 preferable case, described contact comprises fs, subordinate phase and the phase III of successively carrying out, and the condition of described fs comprises that temperature is 100 ℃-130 ℃, and the time is 3-5 hour; The condition of described subordinate phase comprises that temperature is 130 ℃-140 ℃, and the time is 1.5-2.5 hour; The condition of described phase III comprises that temperature is 140 ℃-170 ℃, and the time is 1-2 hour.
According to the present invention, in order to make the temperature that styrene solution and the solution of aliphatic-aromatic copolyester contact the most at the beginning just can be more than 100 ℃, preferably styrene solution is first joined in polymerization reaction kettle, and heat described polymerization reaction kettle, its temperature is remained on be not less than the temperature of 100 ℃.In order to prevent that vinylbenzene from this process, autohemagglutination occuring; under preferable case; namely pass into rare gas element protection in polymerization reaction kettle in heat-processed; described rare gas element is the rare gas element of field of olefin polymerisation routine; at least a as in neutral element gas in 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 as thermal initiation or initiator.Initiator can be selected from least a in Potassium Persulphate, dicumyl peroxide, hydrogen phosphide cumene, benzoyl peroxide or peroxide di-t-butyl, preferably uses hydrogen phosphide cumene.The consumption of initiator is the 0.1-2 % by weight of vinylbenzene total amount in styrene solution, and more preferably the 0.1-0.5 % by weight, most preferably be the 0.1-0.2 % by weight.The present invention preferably uses the mode of thermal initiation.
in addition, can also add auxiliary agents more well known in the art in above-mentioned polymerization system, as protective agent, antioxidant, concrete as, 2, 2, 4-trimethylammonium-1, 2-dihydroquinoline 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 agitator to stir, described agitator can be the agitator of this area routine, as 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 to stir device, 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 described method that removes unreacted monomer and solvent can be the method for this area routine, the present invention is preferably in devolatilizer, under vacuum state, method by flash distillation removes unreacted monomer and solvent, the temperature of described flash distillation can be 180-210 ℃, more preferably 185-195 ℃.
According to following examples, content of the present invention is described further.Carry out various performance tests by 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, take tetrahydrofuran (THF) (THF) as solvent, with the calibration of vinylbenzene standard specimen);
2, percentage of grafting: the biodegradable polyphenylacetylene combination that takes certain mass, with the weight ratio of 1: 50 and acetone-the butanone mixed solvent (wherein, acetone is 1: 1 with the volume ratio of butanone) contact, after stirring, standing 24h, on supercentrifuge with the centrifugal 30min of the speed of 4000r/min, separate and obtain 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 the weight * 100% of the sedimentary weight/polyphenylacetylene combination of gained.
3, socle girder notched Izod impact strength: test according to the method for GB/T1843-2008
4, stretching yield stress: test according to the method for GB/T1040.2-2006
5, biodegradability test: test according to the method for ASTM D5338-92, be that compost buries the sheet method, sample is pressed into 20mm * 20mm, the thick film of (0.2 ± 0.02) mm, imbed in compost after weighing, put into thermostat container, temperature is (55 ± 2) ℃, and humidity is (65 ± 5) %.Take out specimen after 20 weeks, weigh after 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 butanediol copolyester (PBTA)
5, aliphatics content is 75 % by mole, biological degradation rate is 60% (87 days compost), available from BASF AG) join in the 200g ethylbenzene, heat in boiling water bath, stir and PBTA was dissolved fully in 2 hours.
With nitrogen, air in still is replaced fully; 1700g styrene monomer (Yanshan Petrochemical production) and 100g ethylbenzene are added in 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 described agitator is that set square middle and upper part, bottom ribbon combined type stirs device; When the question response temperature reaches 100 ℃, under the protection of nitrogen, the ethylbenzene solution of consoluet PBTA is added in reactor, continue to heat up.120 ℃ of lower polymerizations 4 hours, 130 ℃ of lower polymerizations 2 hours, 157 ℃ of lower polymerizations 1.5 hours.After polymerization is completed, the viscous body of polymerization gained is put into the devolatilizer of 185 ℃, flash distillation rapidly, remove unreacted styrene monomer and solvent ethylbenzene under vacuum state.Obtain 1480g polyphenylacetylene combination P1, wherein, the content of PBTA is 4.9 % by weight.Calculating the transformation efficiency of styrene monomer, is 82.8%.The composition 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 results are shown in 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 composition weight-average molecular weight is 1.25 * 10
5DP1 is carried out Mechanics Performance Testing and biodegradation test, and the results are shown in Table 1.
Comparative Examples 2
The polymer product DP1 that 95.1 weight part Comparative Examples 1 are obtained and the 4.9 weight parts PBTA identical with embodiment 1 that originate mixes, and obtains polystyrene blends DP2.The composition 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 results are shown in Table 1.
Comparative Examples 3
Method according to embodiment 1 prepares polyphenylacetylene combination, and different is, 260 gram PBTA are joined in 200 gram ethylbenzenes, obtains 1620g polymerisate DP3, and wherein, the content of PBTA is 16 % by weight, and cinnamic transformation efficiency is 80%.The composition 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 results are shown in Table 1.
Comparative Examples 4
Method according to embodiment 1 prepares polyphenylacetylene combination, different is, it is in the 1700g vinylbenzene and 300g ethylbenzene of 100 ℃ that 72 gram PBTA solids are directly joined temperature, then carry out polyreaction, obtain 1460g polymerisate DP4, wherein, the content of PBTA is 4.9 % by weight, and cinnamic transformation efficiency is 81.6%.The composition 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 results are shown in Table 1.
Embodiment 2
The PBTA of 60g is added in the 200g ethylbenzene, heat in boiling water bath, stir and PBTA was dissolved fully in 2 hours.
With nitrogen, air in still is replaced fully; 1700g styrene monomer (Yanshan Petrochemical production) and 500g ethylbenzene are added in 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 described agitator is that set square middle and upper part, bottom ribbon combined type stirs device; When the question response temperature reaches 100 ℃, under the protection of nitrogen, the ethylbenzene solution of consoluet PBTA is added in reactor, continue to heat up.105 ℃ of lower polymerizations 5 hours, 135 ℃ of lower polymerizations 2.5 hours, 140 ℃ of lower polymerizations 2 hours.After polymerization is completed, the viscous body of polymerization gained is discharged, put into the devolatilizer of 195 ℃, flash distillation rapidly, remove unreacted styrene monomer and solvent ethylbenzene under vacuum state.Obtain 1420g polyphenylacetylene combination P2, wherein, the content of aliphatics aromatic copolyester is 4.2 % by weight.Calculating the transformation efficiency of styrene monomer, is 80%.The composition 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 results are shown in Table 1.
Embodiment 3
With 85g the terephthalic acid hexylene glycol-(PHTA, available from BASF AG, weight-average molecular weight is 1.2 * 10 to co-hexanodioic acid hexylene glycol copolyesters
5, aliphatics content is 85 % by mole) add in the 200g ethylbenzene, heat in boiling water bath, stir and PHTA was dissolved fully in 3 hours.
With nitrogen, air in still is replaced fully; 1700g styrene monomer (Yanshan Petrochemical production) and 300g ethylbenzene are added in still.Initiating method adopts thermal initiation.Polymeric kettle heats up under the 130rpm/min stir speed (S.S.), and described agitator is that set square middle and upper part, bottom ribbon combined type stirs device; When the question response temperature reaches 100 ℃, under the protection of nitrogen, the ethylbenzene solution of consoluet PHTA is added in reactor, continue to heat up.At 130 ℃ of lower polyase 13s hour, 140 ℃ of lower polymerizations 1.5 hours, 170 ℃ of lower polymerizations 1 hour.After polymerization is completed, the viscous body of polymerization gained is put into the devolatilizer of 190 ℃, flash distillation rapidly, remove unreacted styrene monomer and solvent ethylbenzene under vacuum state.Obtain 1520g polyphenylacetylene combination P3, wherein, the content of aliphatics aromatic copolyester is 5.6 % by weight.Calculating the transformation efficiency of styrene monomer, is 84.2%.The composition 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 results are shown in Table 1.
Embodiment 4
Method according to embodiment 1 prepares polyphenylacetylene combination, and different is, 49 gram PBTA are joined in 200 gram ethylbenzenes, obtains 1460g polymerisate P4, and the content of PBTA is 3.1 % by weight, and cinnamic transformation efficiency is 83%.The composition 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 results are shown in Table 1.
Embodiment 5
Method according to embodiment 1 prepares polyphenylacetylene combination, and different is, 108 gram PBTA are joined in 200 gram ethylbenzenes, obtains 1490g polymerisate P5, and the content of PBTA is 7.2 % by weight, and cinnamic transformation efficiency is 81.3%.The composition 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 results are shown in Table 1.
Embodiment 6
Method according to embodiment 1 prepares polyphenylacetylene combination, and different is, the speed that stirs in polymerization process is 70rpm/ minute, obtains 1460g polymerisate P6, and the content of PBTA is 4.9 % by weight, and cinnamic transformation efficiency is 81.6%.The composition 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 results are shown in Table 1.
Embodiment 7
Method according to embodiment 1 prepares polyphenylacetylene combination, and different is that (PETA, available from BASF AG, weight-average molecular weight is 1.1 * 10 to add 72g terephthalate-co-adipic acid glycol copolyester
5, aliphatics content is 65 % by mole) and replacement 72gPBTA.Obtain 1420 gram polymerisate P7, wherein, the content of PETA is 5.1 % by 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 results are shown in Table 1.
Table 1
By in table 1 result can find out, obtain the polystyrene that DP1 is homopolymerization in 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 is keeping also having possessed considerable biodegradable on the basis of good mechanical property.
Comparative Examples 2 is the mixture of polystyrene and PBTA, 20 all compost rate of weight loss of the mixture that makes in Comparative Examples 2 are only 1.8 % by weight, compare with embodiment 1 very large gap is arranged, only illustrate and to realize the present invention by simple mixing, the polyphenylacetylene combination that obtains in the embodiment of the present invention 1 be by with styrene-grafted to aliphatic-aromatic copolyester, and control reaction under these conditions, just realized obtaining so good biodegradability on the basis that keeps the good mechanical property of polystyrene.
In Comparative Examples 3, the content of PBTA is not within the scope of the present invention, although the biodegradability of the polyphenylacetylene combination that obtains in Comparative Examples 3 is fine, but simultaneously, the socle girder notched Izod impact strength also descends rapidly, the polyphenylacetylene combination that makes does not so possess good mechanical property, greatly reduces the applicability of this polyphenylacetylene combination.
PBTA in Comparative Examples 4 directly carries out polyreaction with solid form and vinylbenzene, as can be seen from Table 1,20 all compost rate of weight loss of this polyphenylacetylene combination are only 2.2 % by weight, this explanation, and PBTA reacts with the form of solution and vinylbenzene could realize the present invention.
Compare with embodiment 1, lower slightly than embodiment 1 of the PBTA content of polymerisate P4 in embodiment 4, its good mechanical properties, but 20 all compost rate of weight loss are reduced to rapidly 5.4 % by weight; The PBTA content of the polymerisate P5 of embodiment 5 is slightly higher than embodiment's 1, and 20 all compost rate of weight loss of P5 reach 24.6 % by weight, but its socle girder notched Izod impact strength but drops to 0.85KJ/m
2, hence one can see that, only has the aliphatic-aromatic copolyester that uses proper content can realize possessing simultaneously considerable biodegradable on the basis of the good mechanical property of maintenance.
Claims (24)
1. a Biodegradable polystyrene composition, is characterized in that, described composition contains the polymkeric substance of polystyrene and vinylbenzene and aliphatic-aromatic copolyester, and the weight-average molecular weight of described composition is 0.8 * 10
5-4.0 * 10
5The biological degradation rate according to ASTM D5338-92 of described composition is the 10-30 % by weight, wherein, described aliphatic-aromatic copolyester is biodegradable aliphatic-aromatic copolyester, take the total amount of described composition as benchmark, in the polymkeric substance of described vinylbenzene and aliphatic-aromatic copolyester, the content of aliphatic-aromatic copolyester part is the 1-15 % by weight; The polymkeric substance of described vinylbenzene and aliphatic-aromatic copolyester is the graftomer of vinylbenzene and aliphatic-aromatic copolyester, and percentage of grafting is 3%-25%, the total mass of the quality of described percentage of grafting=graft copolymer/reaction resulting polymers; Described biological degradation rate is 20 all compost rate of weight loss.
2. composition according to claim 1, wherein, the weight-average molecular weight of described composition is 1.0 * 10
5-3.0 * 10
5, the biological degradation rate according to ASTM D5338-92 of described composition is the 15-25 % by weight.
3. composition according to claim 1, wherein, take the total amount of described composition as benchmark, in the polymkeric substance of described vinylbenzene and aliphatic-aromatic copolyester, the content of aliphatic-aromatic copolyester part is the 2-10 % by weight.
4. composition according to claim 1, wherein, the weight-average molecular weight of described aliphatic-aromatic copolyester is 0.8 * 10
5-1.5 * 10
5
5. the described composition of any one according to claim 1-4, wherein, the percentage of grafting of the polymkeric substance of described vinylbenzene and aliphatic-aromatic copolyester is 5%-20%.
6. the described composition of any one according to claim 1-4, wherein, described aliphatic-aromatic copolyester is comprised of aromatic structure unit and aliphatic structure unit, described aromatic structure unit derives from the binary aliphatic alcohol ester monomer of aromatic binary carboxylic acid, described aliphatic structure unit derives from the binary aliphatic alcohol ester monomer of aliphatic dicarboxylic acid, and take the total mole number of the monomer of copolyesters as benchmark, the content of the binary aliphatic alcohol ester monomer of described aliphatic dicarboxylic acid is greater than 40 % by mole.
7. composition according to claim 6, wherein, described aliphatic dicarboxylic acid is that carbonatoms is the aliphatic dicarboxylic acid of 2-10, described aromatic binary carboxylic acid is that carbonatoms is the aromatic binary carboxylic acid of 8-14, and described aliphatic dihydroxy alcohol is that carbonatoms is the aliphatic dihydroxy alcohol of 2-10.
8. composition according to claim 7, wherein, described aliphatic dicarboxylic acid is hexanodioic acid, and described aromatic binary carboxylic acid is terephthalic acid, and described aliphatic dihydroxy alcohol is at least a in ethylene glycol, propylene glycol, butyleneglycol and hexylene glycol.
9. composition according to claim 8, wherein, described aliphatic-aromatic copolyester is selected from least a in terephthalate-co-adipate glycol copolyesters, terephthaldehyde's acid propylene glycol-co-hexanodioic acid propanediol copolyester, terephthalic acid butyleneglycol-co-hexanodioic acid butanediol copolyester and terephthalic acid hexylene glycol-co-hexanodioic acid hexylene glycol copolyesters.
10. the preparation method of a Biodegradable polystyrene composition, it is characterized in that, the 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 polystyrene composition, wherein, described aliphatic-aromatic copolyester is biodegradable aliphatic-aromatic copolyester, and it is 0.8 * 10 that the condition of described polymerization makes the weight-average molecular weight of composition
5-4.0 * 10
5The biological degradation rate according to ASTM D5338-92 of described composition is the 10-30 % by weight, and the total amount of the described Biodegradable polystyrene composition that the consumption of the solution of aliphatic-aromatic copolyester makes to obtain is benchmark, and in the polymkeric substance of described vinylbenzene and aliphatic-aromatic copolyester, the content of aliphatic-aromatic copolyester part is the 1-15 % by weight; The polymkeric substance of described vinylbenzene and aliphatic-aromatic copolyester is the graftomer of vinylbenzene and aliphatic-aromatic copolyester, and percentage of grafting is 3%-25%, the total mass of the quality of described percentage of grafting=graft copolymer/reaction resulting polymers; Described biological degradation rate is 20 all compost rate of weight loss.
11. method according to claim 10, wherein, it is 1.0 * 10 that the condition of described polymerization makes the weight-average molecular weight of composition
5-3.0 * 10
5The biological degradation rate according to ASTM D5338-92 of described composition is the 15-25 % by weight, and the total amount of the described Biodegradable polystyrene composition that the consumption of the solution of aliphatic-aromatic copolyester makes to obtain is benchmark, and in the polymkeric substance of described vinylbenzene and aliphatic-aromatic copolyester, the content of aliphatic-aromatic copolyester part is the 2-10 % by weight.
12. method according to claim 10, wherein, the cinnamic weight ratio in the aliphatic-aromatic copolyester in the solution of described aliphatic-aromatic copolyester and styrene solution is 1:6-90.
13. method according to claim 12, wherein, the cinnamic weight ratio in the aliphatic-aromatic copolyester in the solution of described aliphatic-aromatic copolyester and styrene solution is 1:7-50.
14. method according to claim 10, wherein, in described styrene solution, cinnamic concentration is the 40-95 % by weight.
15. method according to claim 10, wherein, in described aliphatic-aromatic copolyester solution, the concentration of aliphatic-aromatic copolyester is the 10-40 % by weight.
16. method according to claim 10, wherein, the weight-average molecular weight of described aliphatic-aromatic copolyester is 0.8 * 10
5-1.5 * 10
5
17. the described method of any one according to claim 10-16, wherein, described aliphatic-aromatic copolyester is comprised of aromatic structure unit and aliphatic structure unit, described aromatic structure unit derives from the binary aliphatic alcohol ester monomer of aromatic binary carboxylic acid, described aliphatic structure unit derives from the binary aliphatic alcohol ester monomer of aliphatic dicarboxylic acid, and take the total mole number of the monomer of copolyesters as benchmark, the content of the binary aliphatic alcohol ester monomer of described aliphatic dicarboxylic acid is greater than 40 % by mole.
18. method according to claim 17, wherein, described aliphatic dicarboxylic acid is that carbonatoms is the aliphatic dicarboxylic acid of 2-10, described aromatic binary carboxylic acid is that carbonatoms is the aromatic binary carboxylic acid of 8-14, and described aliphatic dihydroxy alcohol is that carbonatoms is the aliphatic dihydroxy alcohol of 2-10.
19. method according to claim 18, wherein, described aliphatic dicarboxylic acid is hexanodioic acid, and described aromatic binary carboxylic acid is terephthalic acid, and described aliphatic dihydroxy alcohol is at least a in ethylene glycol, propylene glycol, butyleneglycol and hexylene glycol.
20. method according to claim 19, wherein, described aliphatic-aromatic copolyester is selected from least a in terephthalate-co-adipate glycol copolyesters, terephthaldehyde's acid propylene glycol-co-hexanodioic acid propanediol copolyester, terephthalic acid butyleneglycol-co-hexanodioic acid butanediol copolyester and terephthalic acid hexylene glycol-co-hexanodioic acid hexylene glycol copolyesters.
21. the described method of any one according to claim 10-16, wherein, the condition of described contact comprises, under agitation carries out, and temperature is 100-170 ℃, and the time is 5-10 hour.
22. method according to claim 21, wherein, described contact comprises fs, subordinate phase and phase III, and the condition of described fs comprises that temperature is 100 ℃-130 ℃, and the time is 3-5 hour; The condition of described subordinate phase comprises that temperature is 130 ℃-140 ℃, and the time is 1.5-2.5 hour; The condition of described phase III comprises that temperature is 140 ℃-170 ℃, and the time is 1-2 hour.
23. method according to claim 22, wherein, the speed of described stirring is 100-180rpm.
24. the Biodegradable polystyrene composition by the described method preparation of any one in claim 10-23.
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