CN101735588A - PPC (poly(propylene carbonate)), PBAT (poly(butylene adipate/terephthalate)) and PBS (poly(butylene succinate)) blend and preparation method - Google Patents
PPC (poly(propylene carbonate)), PBAT (poly(butylene adipate/terephthalate)) and PBS (poly(butylene succinate)) blend and preparation method Download PDFInfo
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- CN101735588A CN101735588A CN200910258733A CN200910258733A CN101735588A CN 101735588 A CN101735588 A CN 101735588A CN 200910258733 A CN200910258733 A CN 200910258733A CN 200910258733 A CN200910258733 A CN 200910258733A CN 101735588 A CN101735588 A CN 101735588A
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Abstract
The invention relates to PPC (poly(propylene carbonate)), PBAT (poly(butylene adipate/terephthalate)) and PBS (poly(butylene succinate)) blend and a preparation method. The blend is formed by PPC, PBAT, PBS, a blocking agent, lubricant and modified light calcium carbonate, and the preparation method comprises the following steps of: cooling-mixing the PPC, the PBAT, the PBS, the blocking agent, the lubricant and the modified light calcium carbonate in a high-speed mixer under a condition with the temperature not higher than 35 DEG C, and extruding a cooling-mixed material by a screw extruder for pelleting, wherein the temperature for pelleting is not higher than 200 DEG C. The invention has the advantages that the method has simple process, common equipment, and suitability for industrialization production; meanwhile, raw materials used in the method are simple and easy to obtain and can be easily bought in a market; and the blend processed out by the method has greatly increased temperature of sticky clotting higher than that of a pure PPC and greatly improved mechanical performance of the blend larger than that of the pure PPC, broadens the application range of the pure PPC and is completely biodegraded.
Description
Technical field:
The present invention relates to a kind of PPC and PBAT and PBS blend and preparation method, belong to polymer processing field.
Background technology:
Environmental pollution is one of problem demanding prompt solution of facing of current society.Carbonic acid gas is the waste gas that many industrial circles produce, be discharged in the atmospheric layer, not only environment has been caused pollution, and be the waste of carbon resource, one of raw material of carbon dioxide-epoxy propane copolymer is a carbonic acid gas, can stabilizing carbon dioxide by carbonic acid gas and propylene oxide copolyreaction; Simultaneously resulting multipolymer is a kind of nonpoisonous and tasteless, colorless solid that barrier property is excellent, and this multipolymer has the characteristic of complete biodegradable, can replace common plastics to solve " white pollution " problem, therefore has dicyclo guarantor effect.Realize that the suitability for industrialized production of carbon dioxide-epoxy propane polyreaction and the marketization popularization of multipolymer are the targets that entrepreneur and chemical engineers pursue.
Carbonic acid gas and epoxy propane copolymer [Poly (propylene carbonate) below is abbreviated as PPC] are amorphous polymers, and second-order transition temperature (Tg) is about 35 ℃.Temperature is when Tg is above, and the PPC caking that is clamminess influences its storage and transportation; PPC is in vitreous state when Tg is following, and fragility is bigger, and therefore there is very big difficulty in the application of pure PPC.Poly-hexanodioic acid/mutual-phenenyl two acid bromide two alcohol ester [Poly (ButyleneAdipate-co-Terephthalate), below be abbreviated as PBAT] be the terpolymer of hexanodioic acid, terephthalic acid and butyleneglycol, fusing point is about 115 ℃, processing easily, the entanglement that has stronger tenacity to become reconciled, other performance classes is LDPE (new LDPE (film grade)) seemingly, and biodegradation rate is faster arranged; Poly butylene succinate [Poly (Butylene Succinate) below is abbreviated as PBS] fusing point is about 114 ℃, and thermostability and toughness are all better, and degradation speed is faster also arranged.PPC and PBAT, PBS have consistency preferably, the be clamminess temperature of caking of the blend that three's blend obtains is higher than pure PPC, has solved storage and transportation problem, and simultaneously the purer PPC of mechanical property has greatly improved, enlarged its range of application, and can complete biodegradable.
Summary of the invention:
The purpose of this invention is to provide a kind of PPC and PBAT and PBS blend and preparation method, the be clamminess temperature of caking of the blend that obtains with method of the present invention is higher than pure PPC, and the purer PPC of mechanical property has greatly improved simultaneously, and can complete biodegradable.
The objective of the invention is to realize with the following methods:
Blend of the present invention is made up of PPC, PBAT, PBS, end-capping reagent, lubricant and modified and light lime carbonate, wherein: the mass ratio of PBAT and PBS sum and PPC is 10～100: 100, and the shared PBAT of each component among PBAT and the PBS and the ratio of PBS sum are not less than 5% (mass ratio); The mass ratio of end-capping reagent and PPC is 0.2～5: 100; The mass ratio of lubricant and modified and light lime carbonate is 0.5～30: 100; The ratio (mass ratio) of modified and light lime carbonate and polymkeric substance (PPC, PBAT and PBS three's sum) is 1～20: 100.
Described end-capping reagent is a maleic anhydride;
Described lubricant is a kind of in hard ester acid, the epoxy soybean oil or both mixtures;
Described modified and light lime carbonate is that the granular size of light calcium carbonate is between 700～4000 orders through the light calcium carbonate of oleophylic modification.
The preparation method of blend of the present invention is: PPC, PBS and PBAT and end-capping reagent, lubricant and modified and light lime carbonate are carried out cold mixing not being higher than under 35 ℃ the situation in homogenizer, the cold mixed time is 5～10 minutes; The rotating speed of stirrer is 500～1500 rev/mins.
Cold batch mixing is carried out extruding pelletization with screw extrusion press, and the temperature of extruding pelletization is no more than 200 ℃.
Principle of the present invention is: the fusing point of PBAT is about 115 ℃, processing easily, and the entanglement that has stronger tenacity to become reconciled, other performance classes is LDPE seemingly, and biodegradation rate is faster arranged; The PBS fusing point is about 114 ℃, and thermostability and toughness are all better; The blend that PPC and PBAT and PBS blend obtain be clamminess the caking temperature be higher than pure PPC, mechanical property is better than pure PPC; Add a spot of modified and light lime carbonate and can guarantee that PPC does not lump and mixes in mixing process, the while can be improved the performance of blend and be reduced cost; Add end-capping reagent and in the course of processing, do not carry out the zip mode thermolysis in order to guarantee PPC; Add lubricant and be smooth and easy for complete processing, improve working (machining) efficiency; The temperature of extruding pelletization is no more than 200 ℃ and can guarantees in the course of processing PPC and PBAT and not thermolysis of PBS or decompose seldom.
Advantage of the present invention is: the technology of the inventive method is simple, equipment is common.Technology has only two steps of cold mixed extruding pelletization; Employed equipment is very common homogenizer and twin screw extruder or single screw extrusion machine, very suitability for industrialized production.
Method of the present invention employed starting material are simple and easy to.PBAT and PBS are common in the market biological degradation plastics, are easy to buy; The light calcium carbonate granular size just can be used at the common oleophylic modified product of 700～4000 purposes, and is on sale on the market; The processing aid that is added has only two kinds, and what select for use is the very common usual auxiliaries that is easy to get.The be clamminess temperature of caking of the blend that obtains with method of the present invention is higher than pure PPC, and the purer PPC of mechanical property has greatly improved, and has widened the range of application of pure PPC, and can complete biodegradable.
Embodiment:
Embodiment 1:
(covering western new and high technology group company produces to take by weighing PPC, second-order transition temperature is 35 ℃) 2000 grams, maleic anhydride 20 grams, oleophylic modified and light lime carbonate (granular size is 800 orders) 20 grams, hard ester acid 2 grams, PBAT is 100 grams, PBS is 100 grams, joining respectively in the homogenizer, is to stir 5 minutes under 0 ℃ the situation in cold mixed temperature, and the rotating speed of stirrer can be 1500 rev/mins; Emit cold batch mixing, use the single screw extrusion machine extruding pelletization, the highest heating zone Heating temperature is 171 ℃.In baking oven, test the temperature that pellet begins to be clamminess with resulting pellet, carry out sample preparation with the requirement by GB/T17037-1997 in injector of resulting pellet simultaneously, carry out tensile property test, logging test results by the requirement of GB/T 1040-2006 and GB/T 2918-1998 then.
Embodiment 2:
Take by weighing PPC (with embodiment 1) 2000 grams, maleic anhydride 30 grams, oleophylic modified and light lime carbonate (granular size is 1250 orders) 50 grams, epoxy soybean oil 10 grams, PBAT is 200 grams, and PBS is 400 grams, joins in the homogenizer respectively, be to stir 6 minutes under 5 ℃ the situation in cold mixed temperature, the rotating speed of stirrer can be 1000 rev/mins; Emit cold batch mixing, use the single screw extrusion machine extruding pelletization, the highest heating zone Heating temperature is 173 ℃.With temperature and the tensile property that resulting pellet test begins to be clamminess, logging test results (with embodiment 1).
Embodiment 3:
Take by weighing PPC (with embodiment 1) 2000 grams, maleic anhydride 20 grams, light calcium carbonate (granular size is 1250 orders) 100 grams, hard ester acid 20 grams, PBAT is 500 grams, and PBS is 500 grams, joins in the homogenizer respectively, be to stir 10 minutes under 10 ℃ the situation in cold mixed temperature, the rotating speed of stirrer can be 800 rev/mins; Emit cold batch mixing, use the twin screw extruder extruding pelletization, the highest heating zone Heating temperature is 174 ℃.With temperature and the tensile property that resulting pellet test begins to be clamminess, logging test results (with embodiment 1).
Embodiment 4:
Take by weighing PPC (with embodiment 1) 2000 grams, maleic anhydride 30 grams, light calcium carbonate (granular size is 800 orders) 100 grams, epoxy soybean oil 20 grams, PBAT is 800 grams, and PBS is 200 grams, joins in the homogenizer respectively, be to stir 5 minutes under 20 ℃ the situation in cold mixed temperature, the rotating speed of stirrer can be 500 rev/mins; Emit cold batch mixing, use the twin screw extruder extruding pelletization, the highest heating zone Heating temperature is 175 ℃.With temperature and the tensile property that resulting pellet test begins to be clamminess, logging test results (with embodiment 1).
Embodiment 5:
Take by weighing PPC (with embodiment 1) 2000 grams, maleic anhydride 20 grams, light calcium carbonate (granular size is 800 orders) 200 grams, hard ester acid 30 grams, PBAT is 800 grams, and PBS is 800 grams, joins in the homogenizer respectively, be to stir 10 minutes under 25 ℃ the situation in cold mixed temperature, the rotating speed of stirrer can be 1500 rev/mins; Emit cold batch mixing, use the single screw extrusion machine extruding pelletization, the highest heating zone Heating temperature is 176 ℃.With temperature and the tensile property that resulting pellet test begins to be clamminess, logging test results (with embodiment 1).
Embodiment 6:
Take by weighing PPC (with embodiment 1) 2000 grams, maleic anhydride 30 grams, light calcium carbonate (granular size is 1250 orders) 200 grams, epoxy soybean oil 40 grams, PBAT is 1000 grams, and PBS is 1000 grams, joins in the homogenizer respectively, be to stir 5 minutes under 31 ℃ the situation in cold mixed temperature, the rotating speed of stirrer can be 1500 rev/mins; Emit cold batch mixing, use the twin screw extruder extruding pelletization, the highest heating zone Heating temperature is 177 ℃.With temperature and the tensile property that resulting pellet test begins to be clamminess, logging test results (with embodiment 1).
Stearic acid and epoxy soybean oil all can be by the mixture replacings of stearic acid and epoxy soybean oil among the above embodiment, and wherein stearic acid and epoxy soybean oil blending ratio are not limit.PPC also can select the identical product of structure of other manufacturer production for use.
Temperature and tensile property data that embodiment 1～6 resulting pellet begins to be clamminess are as shown in the table, and compare with pure PPC material.
| Pure PPC | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | |
| Begin to be clamminess agglomeration temperature (℃) | ??36 | ??50 | ??56 | ??61 | ??69 | ??72 | ??78 |
| Tensile strength (MPa) | ??1.36 | ??11.5 | ??11.8 | ??11.3 | ??22.0 | ??17.3 | ??19.4 |
| Elongation at break (%) | ??≥800 | ??790 | ??356 | ??235 | ??95 | ??87 | ??65 |
By above-mentioned experimental data as can be known: the purer PPC of the agglomeration temperature that is clamminess of blend of the present invention is significantly improved.In the experimental data of mechanical property, tensile strength has also improved than pure PPC; Elongation at break is in bigger variation range, has widened the range of application of blend.
Claims (8)
1. a PPC and PBAT and PBS blend, it is characterized in that: blend is made up of PPC, PBAT, PBS, end-capping reagent, lubricant and modified and light lime carbonate, wherein: the mass ratio of PBAT and PBS sum and PPC is 10～100: 100, and the shared PBAT of each component among PBAT and the PBS and the ratio of PBS sum are not less than 5% (mass ratio); The mass ratio of end-capping reagent and PPC is 0.2～5: 100; The mass ratio of lubricant and modified and light lime carbonate is 0.5～30: 100; The ratio (mass ratio) of modified and light lime carbonate and polymkeric substance (PPC, PBAT and PBS three's sum) is 1～20: 100.
2. blend according to claim 1 is characterized in that: end-capping reagent is a maleic anhydride.
3. blend according to claim 1 is characterized in that: lubricant is a kind of in hard ester acid, the epoxy soybean oil or both mixtures.
4. blend according to claim 1 is characterized in that: modified and light lime carbonate is that the granular size of light calcium carbonate is between 700～4000 orders through the light calcium carbonate of oleophylic modification.
5. the preparation method of a PPC according to claim 1 and PBAT and PBS blend is characterized in that: PPC, PBAT and PBS and end-capping reagent, lubricant and modified and light lime carbonate are carried out cold mixing not being higher than under 35 ℃ the situation in homogenizer.
6. the preparation method of blend according to claim 5, it is characterized in that: the cold mixed time is 5～10 minutes.
7. the preparation method of blend according to claim 5, it is characterized in that: the rotating speed of stirrer is 500～1500 rev/mins.
8. the preparation method of blend according to claim 5, it is characterized in that: cold batch mixing is carried out extruding pelletization with screw extrusion press, and the temperature of extruding pelletization is no more than 200 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910258733A CN101735588A (en) | 2009-12-11 | 2009-12-11 | PPC (poly(propylene carbonate)), PBAT (poly(butylene adipate/terephthalate)) and PBS (poly(butylene succinate)) blend and preparation method |
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|---|---|---|---|
| CN200910258733A CN101735588A (en) | 2009-12-11 | 2009-12-11 | PPC (poly(propylene carbonate)), PBAT (poly(butylene adipate/terephthalate)) and PBS (poly(butylene succinate)) blend and preparation method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103205100A (en) * | 2013-03-22 | 2013-07-17 | 贵州省复合改性聚合物材料工程技术研究中心 | High-performance PPC (poly(propylene carbonate)) and PBS (poly(butylene succinate) blend and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103205100A (en) * | 2013-03-22 | 2013-07-17 | 贵州省复合改性聚合物材料工程技术研究中心 | High-performance PPC (poly(propylene carbonate)) and PBS (poly(butylene succinate) blend and preparation method thereof |
| CN103205100B (en) * | 2013-03-22 | 2015-07-22 | 贵州省复合改性聚合物材料工程技术研究中心 | High-performance PPC (poly(propylene carbonate)) and PBS (poly(butylene succinate) blend and preparation method thereof |
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Application publication date: 20100616 |