CN101457016A - Blend of carbon dioxide-epoxypropane co-polymer and polycaprolactone and poly butylene succinate and preparation method - Google Patents

Blend of carbon dioxide-epoxypropane co-polymer and polycaprolactone and poly butylene succinate and preparation method Download PDF

Info

Publication number
CN101457016A
CN101457016A CNA2008101869470A CN200810186947A CN101457016A CN 101457016 A CN101457016 A CN 101457016A CN A2008101869470 A CNA2008101869470 A CN A2008101869470A CN 200810186947 A CN200810186947 A CN 200810186947A CN 101457016 A CN101457016 A CN 101457016A
Authority
CN
China
Prior art keywords
ppc
pcl
pbs
blend
ratio
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CNA2008101869470A
Other languages
Chinese (zh)
Other versions
CN101457016B (en
Inventor
刘埃林
汪英杰
赵全胜
张光军
陈有业
蒙昊
王红霞
黄云生
牛丽刚
海山
徐晓燕
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mengxi High Tech Group Co Ltd Inner Mongolia
Original Assignee
Mengxi High Tech Group Co Ltd Inner Mongolia
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mengxi High Tech Group Co Ltd Inner Mongolia filed Critical Mengxi High Tech Group Co Ltd Inner Mongolia
Priority to CN2008101869470A priority Critical patent/CN101457016B/en
Publication of CN101457016A publication Critical patent/CN101457016A/en
Application granted granted Critical
Publication of CN101457016B publication Critical patent/CN101457016B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/04—Particle-shaped
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92895—Barrel or housing

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention provides a blend of a PPC, a PCL and a PBS and the preparation method thereof. The blend comprises PPC, PCL, PBS, an end-capping reagent, a lubricant and a modified precipitated calcium carbonate. The preparation method is to cool mix the substances in a homogenizer according to a certain percentage in a temperature no higher than 35 DEG C and then the cool mixed materials are extrusion granulated in a screw extruder and the temperature for extrusion granulation should not be higher than 170 DEG C. The blend gained from the invention is totally biologically resolved and the comprehensive performances are superior to a single polymer. The raw materials are easy to gain, the equipment is ordinary and the processing technique is simple, therefore the blend is very suitable for industrial production.

Description

A kind of carbon dioxide-epoxypropane copolymer and polycaprolactone and polybutylene succinate blend and preparation method
Technical field
The invention provides PPC and PCL 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 to having caused environmental pollution, and be the waste of carbon resource, one of raw material of carbon dioxide-epoxypropane 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 have dicyclo guarantor effect.Realize that the suitability for industrialized production of carbon dioxide-epoxypropane polyreaction and the marketization popularization of multipolymer are the targets of entrepreneur and chemical engineer's pursuit.Meng Xi group took the lead in realizing producing per year 3000 tons pilot scale chemical industry and produces (patent publication No.: CN1827623A in 2002; CN1895775A; CN1844189A; CN1806975A; CN2865843Y) also product has tentatively been pushed to market.
Carbon dioxide-epoxypropane copolymer (PPC) is an amorphous polymer, second-order transition temperature about 35 ℃, in temperature more than 35 ℃ the time, its store and transportation in caking easily, and the application of downstream producer brought influence, hinder its marketization popularization.
Summary of the invention
The purpose of this invention is to provide can complete biodegradable and a kind of carbon dioxide-epoxypropane copolymer (PPC) and polycaprolactone (PCL) and polybutylene succinate (PBS) blend and preparation method of excellent performance.
A kind of carbon dioxide-epoxypropane copolymer of the present invention (PPC) is formed with polycaprolactone (PCL) and its raw material of polybutylene succinate (PBS) blend: blend is made up of PPC, PCL, PBS, end-capping reagent, lubricant and modified and light lime carbonate.
Wherein the ratio (mass ratio) of PCL and PBS sum and PPC is 5～30: 100; The ratio of PCL and PBS is 10～90: 90～10.
Employed PPC end-capping reagent is a maleic anhydride, and maleic anhydride that is added and the ratio of PPC (mass ratio) are 0.2～5: 100; Lubricant is hard ester acid, epoxy soybean oil or both mixtures (arbitrary proportion), and lubricant that is added and the ratio of light calcium carbonate (mass ratio) are 0.5～30: 100.
The granular size of employed modified and light lime carbonate is at 700～4000 orders, and through the oleophylic modification, the ratio (mass ratio) of light calcium carbonate that is added and polymkeric substance (PPC, PCL and PBS three's sum) is 1～20: 100.
Concrete grammar is: add PPC, PCL and PBS and end-capping reagent, lubricant and modified and light lime carbonate and carried out cold mixed 5-10 minute not being higher than under 35 ℃ the situation in homogenizer, then cold batch mixing is carried out extruding pelletization at screw extrusion press, the temperature of extruding pelletization is no more than 170 ℃.
Principle of the present invention is: polycaprolactone (PCL) softening temperature is more than 55 ℃, and fusing point is 60 ℃, and snappiness is good, and degradation speed is fast, and is good with the PPC consistency; Polybutylene succinate (PBS) fusing point is 114 ℃, and elasticity and toughness are all better, and degradation speed is faster also arranged; With PCL and PBS and PPC blend, can improve the over-all properties of PPC.For keeping PPC is the status of main raw material, and the ratio (mass ratio) of PCL and PBS sum and PPC is for being no more than 30: 100.PPC and PCL and PBS blend can make its excellent properties complementation and improve the second-order transition temperature of 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 170 ℃ and can guarantees in the course of processing not thermolysis of PPC or decompose seldom.
Advantage of the present invention is: excellent product performance and fully can biological degradation; 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.
The inventive method employed starting material are simple and easy to.PCL and PBS are easy to buy on market; Granular size on the light calcium carbonate market just can be used at the common oleophylic modified product of 700～4000 purposes; 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.End-capping reagent is maleic anhydride, the maleic anhydride that is added and the ratio of PPC
(mass ratio) is 0.2～5: 100; Lubricant is hard ester acid, epoxy soybean oil or both mixtures (arbitrary proportion), and lubricant that is added and the ratio of light calcium carbonate (mass ratio) are 0.5～30: 100.The granule performance that processes is better than pure PPC.
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, PCL is 50 grams, PBS is 50 grams, joins respectively in the homogenizer, stirs 5～10 minutes being no more than under 35 ℃ the situation, according to the equipment situation, the rotating speed of stirrer can be 500～1500 rev/mins; Emit cold batch mixing, carry out extruding pelletization with single screw extrusion machine or twin screw extruder, the Heating temperature in each district is according to extruding the situation setting, the highlyest is no more than 170 ℃.The pellet that obtains is measured with differential scanning calorimeter (DSC), and getting second-order transition temperature is 51.2 ℃.
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, PCL are 100 grams, and PBS is 100 grams, and cold mixed extruding pelletization situation is with embodiment 1.The pellet that obtains is measured with differential scanning calorimeter (DSC), and getting second-order transition temperature is 57.05 ℃.
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, PCL is 160 grams, and PBS is 40 grams, and cold mixed extruding pelletization situation is with embodiment 1.The pellet that obtains is measured with differential scanning calorimeter (DSC), and getting second-order transition temperature is 57.3 ℃.
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, PCL are 40 grams, and PBS is 160 grams, and cold mixed extruding pelletization situation is with embodiment 1.The pellet that obtains is measured with differential scanning calorimeter (DSC), and getting second-order transition temperature is 58.03 ℃.
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, PCL is 200 grams, and PBS is 200 grams, and cold mixed extruding pelletization situation is with embodiment 1.The pellet that obtains is measured with differential scanning calorimeter (DSC), and getting second-order transition temperature is 58.22 ℃.
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, PCL are 300 grams, and PBS is 300 grams, and cold mixed extruding pelletization situation is with embodiment 1.The pellet that obtains is measured with differential scanning calorimeter (DSC), and getting second-order transition temperature is 58.88 ℃.
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.
Used PPC remove to cover western new and high technology group company and produces, and second-order transition temperature is that the like product of other manufacturer production also can use outside 35 ℃ the product.

Claims (6)

1, a kind of carbon dioxide-epoxypropane copolymer (PPC) and polycaprolactone (PCL) and polybutylene succinate (PBS) blend, it is characterized in that: blend is made up of PPC, PCL, PBS, end-capping reagent, lubricant and modified and light lime carbonate.
2, blend according to claim 1 is characterized in that: the ratio (mass ratio) of PCL and PBS sum and PPC is 5～30: 100; The ratio of PCL and PBS is 10～90: 90～10.
3, according to the described blend of claim 1, it is characterized in that: employed PPC end-capping reagent is a maleic anhydride, and maleic anhydride that is added and the ratio of PPC (mass ratio) are 0.2～5: 100; Lubricant is hard ester acid, epoxy soybean oil or both mixtures (arbitrary proportion), and lubricant that is added and the ratio of light calcium carbonate (mass ratio) are 0.5～30: 100.
4, according to the described blend of claim 1, the granular size that it is characterized in that employed modified and light lime carbonate is at 700～4000 orders, and through the oleophylic modification, the ratio (mass ratio) of light calcium carbonate that is added and polymkeric substance (PPC, PCL and PBS three's sum) is 1～20: 100.
5, a kind of right for preparing is as requiring the method for 1 described blend, it is characterized in that: at first PPC, PCL, PBS, end-capping reagent, lubricant and modified and light lime carbonate, cold mixed in homogenizer in proportion, cold mixed temperature is not higher than 35 ℃, then cold batch mixing is carried out extruding pelletization at screw extrusion press, the temperature of extruding pelletization is no more than 170 ℃.
6, method as claimed in claim 5, cold mixed temperature is no more than 35 ℃, and the cold mixed time is 5～10 minutes, and according to the equipment situation, the rotating speed of stirrer can be 500～1500 rev/mins.
CN2008101869470A 2008-12-07 2008-12-07 Blend of carbon dioxide-epoxypropane co-polymer and polycaprolactone and poly butylene succinate and preparation method Expired - Fee Related CN101457016B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2008101869470A CN101457016B (en) 2008-12-07 2008-12-07 Blend of carbon dioxide-epoxypropane co-polymer and polycaprolactone and poly butylene succinate and preparation method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2008101869470A CN101457016B (en) 2008-12-07 2008-12-07 Blend of carbon dioxide-epoxypropane co-polymer and polycaprolactone and poly butylene succinate and preparation method

Publications (2)

Publication Number Publication Date
CN101457016A true CN101457016A (en) 2009-06-17
CN101457016B CN101457016B (en) 2012-03-07

Family

ID=40768150

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2008101869470A Expired - Fee Related CN101457016B (en) 2008-12-07 2008-12-07 Blend of carbon dioxide-epoxypropane co-polymer and polycaprolactone and poly butylene succinate and preparation method

Country Status (1)

Country Link
CN (1) CN101457016B (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101851409A (en) * 2010-06-09 2010-10-06 内蒙古蒙西高新技术集团有限公司 Mixture of PPC (polyenyl phosphophatidyl choline), PHBV (Polyhydroxybutyrate Valerate), PLA (Poly lactic Acid), PBS (Polybutadiene Styrene), PBAT (polybutylene adipate terephthalate) and PCL (polycaprolactone) and preparation method thereof
CN101935445A (en) * 2010-09-21 2011-01-05 中国科学院长春应用化学研究所 Carbon dioxide-propylene oxide copolymer composition
CN101735587B (en) * 2009-12-11 2012-12-05 内蒙古蒙西高新技术集团有限公司 PPC (poly(propylene carbonate)), PBAT (poly(butylene adipate/terephthalate)) and PLA (poly(lactic acid)) blend and preparation method
CN101962470B (en) * 2009-07-22 2012-12-26 中国海洋石油总公司 Biodegradable polypropylene carbonate composite material and preparation method thereof
WO2014205920A1 (en) * 2013-06-28 2014-12-31 Zhang Chunhua Biodegradable resin composition
CN117603570A (en) * 2024-01-24 2024-02-27 山东联欣环保科技有限公司 Dimensionally stable polycarbonate compositions

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1259371C (en) * 2002-12-12 2006-06-14 中山大学 Degradable polymer/natural mineal filler composite material and preparation method thereof
CN1896142A (en) * 2005-07-14 2007-01-17 吉林金源北方科技发展有限公司 Medical degradable composite material
CN1923892B (en) * 2005-08-30 2010-11-10 吉林金源北方科技发展有限公司 Degradation type composite material

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101962470B (en) * 2009-07-22 2012-12-26 中国海洋石油总公司 Biodegradable polypropylene carbonate composite material and preparation method thereof
CN101735587B (en) * 2009-12-11 2012-12-05 内蒙古蒙西高新技术集团有限公司 PPC (poly(propylene carbonate)), PBAT (poly(butylene adipate/terephthalate)) and PLA (poly(lactic acid)) blend and preparation method
CN101851409A (en) * 2010-06-09 2010-10-06 内蒙古蒙西高新技术集团有限公司 Mixture of PPC (polyenyl phosphophatidyl choline), PHBV (Polyhydroxybutyrate Valerate), PLA (Poly lactic Acid), PBS (Polybutadiene Styrene), PBAT (polybutylene adipate terephthalate) and PCL (polycaprolactone) and preparation method thereof
CN101851409B (en) * 2010-06-09 2012-02-22 内蒙古蒙西高新技术集团有限公司 Mixture of PPC (polyenyl phosphophatidyl choline), PHBV (Polyhydroxybutyrate Valerate), PLA (Poly lactic Acid), PBS (Polybutadiene Styrene), PBAT (polybutylene adipate terephthalate) and PCL (polycaprolactone) and preparation method thereof
CN101935445A (en) * 2010-09-21 2011-01-05 中国科学院长春应用化学研究所 Carbon dioxide-propylene oxide copolymer composition
CN101935445B (en) * 2010-09-21 2012-05-23 中国科学院长春应用化学研究所 Carbon dioxide-propylene oxide copolymer composition
WO2014205920A1 (en) * 2013-06-28 2014-12-31 Zhang Chunhua Biodegradable resin composition
CN117603570A (en) * 2024-01-24 2024-02-27 山东联欣环保科技有限公司 Dimensionally stable polycarbonate compositions

Also Published As

Publication number Publication date
CN101457016B (en) 2012-03-07

Similar Documents

Publication Publication Date Title
CN101457016B (en) Blend of carbon dioxide-epoxypropane co-polymer and polycaprolactone and poly butylene succinate and preparation method
CN101724242B (en) Blend of PPC, PBAT, PCL and PLA and preparation method thereof
CN101712775B (en) Preparation method of starch-base biodegradation material
CN101698709B (en) Polypropylene modified material for degradable disposable tableware and preparation method thereof
CN101735587B (en) PPC (poly(propylene carbonate)), PBAT (poly(butylene adipate/terephthalate)) and PLA (poly(lactic acid)) blend and preparation method
CN102391628B (en) Polylactic acid/ polyamide 11 alloy material
TW202009267A (en) Hydrophobic thermoplastic Starch and method for manufacturing the same
CN101724251B (en) Blend of PPC and PBAT and preparation method thereof
CN101851409B (en) Mixture of PPC (polyenyl phosphophatidyl choline), PHBV (Polyhydroxybutyrate Valerate), PLA (Poly lactic Acid), PBS (Polybutadiene Styrene), PBAT (polybutylene adipate terephthalate) and PCL (polycaprolactone) and preparation method thereof
CN100374270C (en) Production technology of comixed biodegradable material
CN110938291A (en) Polylactic acid composite material and preparation method thereof
CN101486829A (en) Method for improving poly(propylene carbonate) glass transition temperature by nano calcium carbonate filling modification
CN113234304A (en) Biodegradable film material and preparation method of film
CN101486832A (en) Carbon dioxide - epoxypropane copolymer and polycaprolactone blend and preparation
CN113461930B (en) Anhydride and epoxy polymer chain-extending tackifier and preparation method and application thereof
CN107383255A (en) A kind of transparent wide molecular weight distribution atactic copolymerized polypropene plastics sucking moulding is resin dedicated and preparation method
CN101759896A (en) Polyethylene modified material for degradable garbage bags and preparation method thereof
CN101724244A (en) Blend of PPC, PBAT and PCL and preparation method thereof
CN101486833A (en) Method for improving glass transition temperature of poly(propylene carbonate)
CN105086393B (en) Plastic allowing PLA to be fully degraded and production method thereof
CN101724243A (en) Blend of PPC and PLA and preparation method thereof
CN101486830B (en) Light calcium carbonate filling modification preparation of carbon dioxide-epoxypropane copolymer
CN101724248B (en) Blend of PPC, PBAT, PCL and PBS and preparation method thereof
CN101724250B (en) Blend of PPC, PBAT, PLA and PBS and preparation method thereof
CN101724249B (en) Blend of PPC, PBAT, PCL, PBS and PLA and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
DD01 Delivery of document by public notice
DD01 Delivery of document by public notice

Addressee: Xu Xiaoyan

Document name: payment instructions

CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20120307

Termination date: 20211207