CN103467609B - 一种纳米羧甲基淀粉的制备方法 - Google Patents
一种纳米羧甲基淀粉的制备方法 Download PDFInfo
- Publication number
- CN103467609B CN103467609B CN201310468497.5A CN201310468497A CN103467609B CN 103467609 B CN103467609 B CN 103467609B CN 201310468497 A CN201310468497 A CN 201310468497A CN 103467609 B CN103467609 B CN 103467609B
- Authority
- CN
- China
- Prior art keywords
- starch
- carboxymethyl starch
- screw extruder
- nano
- oven
- 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.)
- Active
Links
- 229920002472 Starch Polymers 0.000 title claims abstract description 62
- 239000008107 starch Substances 0.000 title claims abstract description 62
- 235000019698 starch Nutrition 0.000 title claims abstract description 62
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 239000007921 spray Substances 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000001125 extrusion Methods 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 235000011187 glycerol Nutrition 0.000 claims description 5
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 claims description 4
- 239000004902 Softening Agent Substances 0.000 claims description 4
- 238000010298 pulverizing process Methods 0.000 claims description 4
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 240000003183 Manihot esculenta Species 0.000 claims description 2
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 235000013312 flour Nutrition 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- -1 methane amide Chemical class 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 11
- 239000003814 drug Substances 0.000 abstract description 4
- 235000013305 food Nutrition 0.000 abstract description 4
- 238000006467 substitution reaction Methods 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract description 2
- 239000004014 plasticizer Substances 0.000 abstract 2
- 239000003431 cross linking reagent Substances 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 239000002105 nanoparticle Substances 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000002904 solvent Substances 0.000 description 2
- 230000010148 water-pollination Effects 0.000 description 2
- 229920000881 Modified starch Polymers 0.000 description 1
- 239000004368 Modified starch Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 235000019426 modified starch Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
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
- B29C48/25—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
- 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
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
-
- 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
- B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
- B29C48/875—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling for achieving a non-uniform temperature distribution, e.g. using barrels having both cooling and heating zones
-
- 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
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
-
- 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
- B29C2948/92885—Screw or gear
-
- 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)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
本发明公开了一种纳米羧甲基淀粉的制备方法。该方法以原淀粉为原料，加入增塑剂，一氯乙酸，碱化剂，在高速搅拌机混合均匀，通过七节筒体的双螺杆挤压机挤压，在第五节筒体处以液体喷枪注入交联剂，物料挤压后通过挤压机出料口，再经干燥、冷却、粉碎后得到纳米羧甲基淀粉。本发明制得的纳米羧甲基淀粉，取代度0.05-0.6，平均粒径80-350nm，粒径分布均匀，且纳米颗粒表面光滑平整，在国内首次用双螺杆挤压机生产了纳米羧甲基淀粉，为纳米羧甲基淀粉在造纸、食品和医药等领域的应用提供了基础。
Description
技术领域
本发明属于淀粉变性技术领域，特别涉及一种纳米羧甲基淀粉的制备方法。
背景技术
淀粉是一种重要的可再生和可生物降解的天然资源，淀粉分子上有很多羟基，在一定温度条件下，能吸水膨胀而糊化，具有一定的粘性和粘着力，在工业上有较广泛的应用。
羧甲基淀粉(Carboxymethyl starch)是一类重要的变性淀粉，含有负电荷基团羧基，使其具备了许多独特的性质，如易溶于水，糊液粘度稳定且透明度高，分散性、成膜性好等，目前广泛用于食品、医药、纺织、造纸等行业中。制备羧甲基淀粉的方法主要有：水媒法、溶媒法和干法，其中水媒法只能制备取代度及粘度较低的产品，且产物后处理困难，耗水量大；溶媒法能制备高取代度且取代基分布较均匀的产品，但制备时间长，生产成本高；干法存在淀粉和反应试剂之间难以混合均匀，产品取代基分布不均匀等问题。
采用双螺杆挤压技术生产纳米羧甲基淀粉，工艺简单，无污水产生，反应效率高，生产成本低。挤压法生产纳米羧甲基淀粉，在对淀粉进行羧甲基化的同时，还可使淀粉糊化，并通过挤压后期添加交联剂，对析出的淀粉分子进行干交联，从而形成稳定的纳米级羧甲基淀粉。
本发明为实现采用双螺杆挤压技术大规模生产纳米羧甲基淀粉奠定了很好的基础，为纳米羧甲基淀粉应用于造纸、食品和医药等领域奠定基础。
发明内容
本发明的目的是提供一种纳米羧甲基淀粉的挤压制备方法。
本发明的技术方案为：一种纳米羧甲基淀粉的制备方法，以原淀粉为原料，加入增塑剂，一氯乙酸，碱化剂，在高速搅拌机混合均匀，通过七节筒体的双螺杆挤压机挤压，在第五节筒体处以液体喷枪注入交联剂，物料挤压后通过挤压机出料口，再经干燥、冷却、粉碎后得到纳米羧甲基淀粉；
1)制备混合料
称取原淀粉，按比例加入塑化剂，原淀粉绝干量的5％-30％的一氯乙酸，碱化剂，加蒸馏水调节体系水分含量至20-30％，在转速为1500-2000r/min的高速搅拌机中混合均匀；
2)七节筒体的双螺杆挤压机挤压条件控制
螺杆转速250-350rpm，挤压机七段温度分别设定为60-75℃，80-90℃，100-110℃，110-115℃，115-120℃，120-125℃，125-130℃，挤压机出料口的模头孔径为5-10mm；
3)挤压
将混合料放入双螺杆挤压机，经由喂料器进入挤压机内挤压，开始进行淀粉的羧甲基化，并在挤压机第五节筒体处以液体喷枪注入交联剂，使已塑化羧甲基化的淀粉分子的碳六原子通过交联剂的官能团互相连接，形成稳定的纳米羧甲基淀粉微粒；
4)干燥、粉碎
将通过双螺杆挤压机挤压反应后所得产物放入烘箱，烘箱温度30-45℃，对挤出物进行烘干，在室温下冷却，用粉碎机粉碎，得纳米羧甲基淀粉产品。
本发明所用的原淀粉为木薯淀粉、玉米淀粉中的一种。
所述的增塑剂是甲酰胺、水、甘油、尿素中的一种或两种混合物，用量为原淀粉绝干量的5％-15％。
所述的碱化剂为氢氧化钠、氢氧化钾中的一种或两种混合物，用量为原淀粉绝干量的2％-15％。
所述的交联剂为环氧氯丙烷、乙二醛、甲醛中的一种或两种混合物，用量为原淀粉绝干量的0.5％-5％。
本发明的有益效果：本发明采用双螺杆挤压技术生产纳米羧甲基淀粉，原料易得，生产工艺简单，生产成本降低，绿色无污染，可生物降解。
本发明制得的产品纳米羧甲基淀粉，取代度0.05-0.6，平均粒径80-350nm，粒径分布均匀，且纳米颗粒表面光滑平整，在国内首次用双螺杆挤压机生产了纳米羧甲基淀粉，为纳米羧甲基淀粉在造纸、食品和医药等领域的应用提供了基础。
具体实施方式
实施例1：
称取10kg玉米淀粉，加入甘油800g，一氯乙酸800g，氢氧化钠500g，加蒸馏水调节体系水分含量至25％，在转速为1500r/min的高速搅拌机混合均匀。调节双螺杆挤压机螺杆转速300rpm，挤压机七段温度分别设定为65℃，80℃，100℃，110℃，115℃，120℃，130℃，挤压机出料口的模头孔径为5mm。将混合料经由喂料器进入双螺杆挤压机内挤压，并在挤压机第五节筒体以液体喷枪注入交联剂乙二醛100g。将挤出物放入烘箱，烘箱温度35℃，对挤出物进行烘干，在室温下冷却，用粉碎机粉碎，得纳米羧甲基淀粉产品。
实施例2：
称取10kg玉米淀粉，加入甘油600g，一氯乙酸1000g，氢氧化钠800g，加蒸馏水调节体系水分含量至27％，在转速为1800r/min的高速搅拌机混合均匀。调节双螺杆挤压机螺杆转速320rpm，挤压机七段温度分别设定为65℃，85℃，105℃，115℃，120℃，125℃，130℃，挤压机出料口的模头孔径为6mm。将混合料经由喂料器进入双螺杆挤压机内挤压，并在挤压机第五节筒体以液体喷枪注入交联剂乙二醛120g。将挤出物放入烘箱，烘箱温度35℃，对挤出物进行烘干，在室温下冷却，用粉碎机粉碎，得纳米羧甲基淀粉产品。
实施例3：
称取15kg玉米淀粉，加入甘油1500g，一氯乙酸1800g，氢氧化钠1500g，加蒸馏水调节体系水分含量至30％，在转速为2000r/min的高速搅拌机混合均匀。调节双螺杆挤压机螺杆转速350rpm，挤压机七段温度分别设定为70℃，80℃，100℃，110℃，120℃，125℃，130℃，挤压机出料口的模头孔径为5mm。将混合料经由喂料器进入双螺杆挤压机内挤压，并在挤压机第五节筒体以液体喷枪注入交联剂环氧氯丙烷300g。将挤出物放入烘箱，烘箱温度35℃，对挤出物进行烘干，在室温下冷却，用粉碎机粉碎，得纳米羧甲基淀粉产品。
Claims (4)
1.一种纳米羧甲基淀粉的制备方法，其特征在于：以原淀粉为原料，加入增塑剂，一氯乙酸，碱化剂氢氧化钠，在高速搅拌机混合均匀，通过七节筒体的双螺杆挤压机挤压，在第五节筒体处以液体喷枪注入交联剂，物料挤压后通过挤压机出料口，再经干燥、冷却、粉碎后得到纳米羧甲基淀粉；主要步骤为：
1)制备混合料：称取原淀粉，按比例加入塑化剂，原淀粉绝干量的5％-30％一氯乙酸，原淀粉绝干量的2％-15％氢氧化钠碱化剂，加蒸馏水调节体系水分含量至20-30％，在转速为1500-2000r/min的高速搅拌机中混合均匀；
2)七节筒体的双螺杆挤压机挤压条件控制：螺杆转速250-350rpm，挤压机七段温度分别设定为60-75℃，80-90℃，100-110℃，110-115℃，115-120℃，120-125℃，125-130℃，挤压机出料口的模头孔径为5-10mm；
3)挤压：将混合料放入双螺杆挤压机，经由喂料器进入挤压机内挤压，开始进行淀粉的羧甲基化，并在挤压机第五节筒体处以液体喷枪注入交联剂，使已塑化羧甲基化的淀粉分子的碳六原子通过交联剂的官能团互相连接，形成稳定的纳米羧甲基淀粉微粒；
4)干燥、粉碎：将通过双螺杆挤压机挤压反应后所得产物放入烘箱，烘箱温度30-45℃，对挤出物进行烘干，在室温下冷却，用粉碎机粉碎，得纳米羧甲基淀粉产品。
2.根据权利要求1所述的纳米羧甲基淀粉的制备方法，其特征在于：所述的原淀粉为木薯淀粉、玉米淀粉中的一种。
3.根据权利要求1所述的纳米羧甲基淀粉的制备方法，其特征在于：所述的增塑剂是甲酰胺、水、甘油、尿素中的一种或两种混合物，用量为原淀粉绝干量的5％-15％。
4.根据权利要求1所述的纳米羧甲基淀粉的制备方法，其特征在于：所述的交联剂为环氧氯丙烷、乙二醛、甲醛中的一种或两种混合物，用量为原淀粉绝干量的0.5％-5％。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310468497.5A CN103467609B (zh) | 2013-10-10 | 2013-10-10 | 一种纳米羧甲基淀粉的制备方法 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310468497.5A CN103467609B (zh) | 2013-10-10 | 2013-10-10 | 一种纳米羧甲基淀粉的制备方法 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103467609A CN103467609A (zh) | 2013-12-25 |
| CN103467609B true CN103467609B (zh) | 2015-08-12 |
Family
ID=49792669
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310468497.5A Active CN103467609B (zh) | 2013-10-10 | 2013-10-10 | 一种纳米羧甲基淀粉的制备方法 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103467609B (zh) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20170016386A (ko) * | 2014-06-02 | 2017-02-13 | 테티스, 아이엔씨. | 개질된 생체중합체, 및 이의 제조 및 사용 방법 |
| CN105694757B (zh) * | 2016-03-16 | 2018-01-19 | 湖南思达奇生物科技有限公司 | 一种生物纳米胶的制备方法 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101838405A (zh) * | 2008-10-14 | 2010-09-22 | 哈尔滨长方圆高科技环保实业有限公司 | 全降解食品包装材料的工业化生产方法 |
| CN101928403B (zh) * | 2010-05-21 | 2012-01-25 | 吉林大学 | 一种热塑性淀粉制品的表面交联处理方法 |
| CN103131350B (zh) * | 2013-03-28 | 2015-06-03 | 成都新柯力化工科技有限公司 | 一种熟胶粉及其制备方法 |
-
2013
- 2013-10-10 CN CN201310468497.5A patent/CN103467609B/zh active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN103467609A (zh) | 2013-12-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103435708B (zh) | 一种纳米两性淀粉的制备方法 | |
| CN103435855B (zh) | 一种纳米阳离子淀粉的制备方法 | |
| CN102108196B (zh) | 一种聚乳酸可降解材料的制备方法 | |
| CN103865284B (zh) | 环保生物质材料及其制备方法 | |
| CN105011346B (zh) | 一种再造烟草薄片丝的制备方法 | |
| CN101456916B (zh) | 一种脂肪酸淀粉酯的制备方法与应用 | |
| CN105315688A (zh) | 一种秸秆生物质的改性及其使用方法 | |
| CN105038284A (zh) | 一种应用木质纤维制备木塑复合材料的方法 | |
| CN102825791B (zh) | 一种木塑复合材料的生产方法 | |
| CN106543675A (zh) | 一种石墨烯3d打印线材的制备方法 | |
| CN104387621A (zh) | 一种热塑性淀粉材料及其制备工艺 | |
| CN101831152A (zh) | 一种热塑性完全生物降解塑料 | |
| CN109054104A (zh) | 一种竹粉填充增强的淀粉基可降解复合发泡材料的制备方法 | |
| CN102627829B (zh) | 利用废旧abs塑料制作的复合纤维板及制备方法 | |
| CN107698810A (zh) | 一种生物质全降解包装材料的制备方法 | |
| CN103467609B (zh) | 一种纳米羧甲基淀粉的制备方法 | |
| CN103496151B (zh) | 一种造纸涂布用纳米淀粉的制备方法 | |
| CN105694757B (zh) | 一种生物纳米胶的制备方法 | |
| CN105542415A (zh) | 一种3d打印用pla木塑复合材料及其制备方法 | |
| CN102838880B (zh) | 一种利用可再生资源生产环保型木塑复合材料的方法 | |
| CN107043550A (zh) | 一种环保纸杯的制备方法 | |
| CN107214929A (zh) | 交联聚合物纳米淀粉颗粒及其制备方法 | |
| CN109705513A (zh) | 一种高性能3d打印用生物复合材料及其制备方法 | |
| CN202727317U (zh) | 可降解塑料双螺杆挤出机 | |
| CN101891832A (zh) | 一种新型无碱均相生产氧化淀粉方法 |
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 |