WO2022214057A1 - Composition de plastique et son utilisation, pièce en plastique, son procédé de préparation et son utilisation - Google Patents
Composition de plastique et son utilisation, pièce en plastique, son procédé de préparation et son utilisation Download PDFInfo
- Publication number
- WO2022214057A1 WO2022214057A1 PCT/CN2022/085723 CN2022085723W WO2022214057A1 WO 2022214057 A1 WO2022214057 A1 WO 2022214057A1 CN 2022085723 W CN2022085723 W CN 2022085723W WO 2022214057 A1 WO2022214057 A1 WO 2022214057A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- antibacterial
- plastic
- plastic composition
- masterbatch
- composition according
- Prior art date
Links
- 239000004033 plastic Substances 0.000 title claims abstract description 104
- 239000000203 mixture Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 91
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 39
- 239000000463 material Substances 0.000 claims abstract description 22
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 13
- 239000003651 drinking water Substances 0.000 claims abstract description 11
- 235000020188 drinking water Nutrition 0.000 claims abstract description 11
- 229920000642 polymer Polymers 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims description 17
- 239000004480 active ingredient Substances 0.000 claims description 15
- -1 polyhexamethylene monoguanidine Polymers 0.000 claims description 14
- VAZJLPXFVQHDFB-UHFFFAOYSA-N 1-(diaminomethylidene)-2-hexylguanidine Polymers CCCCCCN=C(N)N=C(N)N VAZJLPXFVQHDFB-UHFFFAOYSA-N 0.000 claims description 9
- 238000001746 injection moulding Methods 0.000 claims description 9
- 229920002413 Polyhexanide Polymers 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 abstract description 12
- 239000004332 silver Substances 0.000 abstract description 12
- 238000001556 precipitation Methods 0.000 abstract description 9
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 7
- 239000002244 precipitate Substances 0.000 abstract description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 241000894006 Bacteria Species 0.000 description 5
- 239000003242 anti bacterial agent Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000009519 fu-yuan Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- AVWOEAVWVDLXMA-UHFFFAOYSA-N 1-(diaminomethylidene)guanidine;nitric acid Chemical compound O[N+]([O-])=O.NC(N)=NC(N)=N AVWOEAVWVDLXMA-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- ZILVNHNSYBNLSZ-UHFFFAOYSA-N 2-(diaminomethylideneamino)guanidine Chemical group NC(N)=NNC(N)=N ZILVNHNSYBNLSZ-UHFFFAOYSA-N 0.000 description 1
- XNCOSPRUTUOJCJ-UHFFFAOYSA-N Biguanide Chemical compound NC(N)=NC(N)=N XNCOSPRUTUOJCJ-UHFFFAOYSA-N 0.000 description 1
- 229940123208 Biguanide Drugs 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007922 dissolution test Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
Definitions
- the invention relates to the field of antibacterial materials for drinking water equipment, in particular to a plastic composition and application thereof, a plastic part and a preparation method thereof, and the application of the plastic part in the preparation of antibacterial drinking water equipment.
- the purpose of the present invention is to overcome the defects of the prior art that the small molecule organic antibacterial agent is easy to migrate and precipitate, the thermal stability is poor, and the precipitation of heavy metals such as silver in the silver-loaded antibacterial material exceeds the standard.
- the first aspect of the present invention provides a plastic composition
- the plastic composition contains plastic raw materials and an antibacterial masterbatch in a weight ratio of 100:1-10, and the antibacterial masterbatch is grafted with antibacterial activity.
- the polymer of the ingredients, the graft ratio of the antibacterial active ingredients in the antibacterial masterbatch is 1-25%;
- the antibacterial master batch is selected from at least one of polyhexamethylene monoguanidine grafted polymer and polyhexamethylene biguanide grafted polymer; the polyhexamethylene monoguanidine salt and The salts of the polyhexamethylene biguanide salts are each independently selected from at least one of hydrochloride, sulfate, nitrate, and phosphate.
- R is a mono/biguanidine salt group grafted onto the polymer molecular chain, and each T is independently selected from hydrogen, methyl, ethyl, and phenyl.
- the second aspect of the present invention provides the application of the plastic composition described in the first aspect above in the preparation of plastic parts.
- a third aspect of the present invention provides a plastic component, and the material for forming the plastic component is the plastic composition described in the first aspect.
- a fourth aspect of the present invention provides a method for preparing the plastic parts described in the third aspect, the method comprising:
- a fifth aspect of the present invention provides the application of the plastic parts described in the third aspect in the preparation of antibacterial drinking water equipment.
- the first aspect of the present invention provides a plastic composition
- the plastic composition contains plastic raw materials and antibacterial masterbatch in a weight ratio of 100:1-10, and the antibacterial masterbatch is grafted with A polymer of antibacterial active ingredients, the graft ratio of the antibacterial active ingredients in the antibacterial master batch is 1-25%;
- the antibacterial master batch is selected from at least one of polyhexamethylene monoguanidine grafted polymer and polyhexamethylene biguanide grafted polymer; the polyhexamethylene monoguanidine salt and The salts of the polyhexamethylene biguanide salts are each independently selected from at least one of hydrochloride, sulfate, nitrate, and phosphate.
- the graft polymer antibacterial plastic composition provided by the present invention binds the organic antibacterial active ingredients to the polymer molecular chain through chemical bonds, and the antibacterial active ingredients can maintain a good antibacterial effect without long-term use.
- the phenomenon of migration and precipitation occurs in the antibacterial agent, thus overcoming the shortcomings of easy migration and precipitation of organic antibacterial agents and poor thermal stability.
- the graft ratio of the antibacterial active ingredient in the antibacterial masterbatch is 10-20%.
- the graft ratio of the antibacterial active ingredient in the antibacterial masterbatch is 10-15%.
- the content weight ratio of the plastic raw material and the antibacterial masterbatch in the plastic composition is 100:2-8.
- the content weight ratio of the plastic raw material and the antibacterial masterbatch in the plastic composition is 100:4.5-7.5.
- the content weight ratio of the plastic raw material and the antibacterial masterbatch in the plastic composition is 100:4.5-7.5, the plastic parts with better plastic performance and antibacterial ability can be obtained.
- the plastic raw material is selected from at least one of PP and PE.
- the polymer matrix forming the antibacterial masterbatch is selected from at least one of PP and PE.
- the second aspect of the present invention provides the application of the plastic composition described in the first aspect in the preparation of plastic parts.
- the third aspect of the present invention provides a plastic component, and the material for forming the plastic component is the plastic composition described in the first aspect.
- the corresponding substances involved in the plastic parts of the third aspect of the present invention are the corresponding substances in the plastic composition described in the first aspect of the present invention, and those skilled in the art will not repeat the corresponding substances in this aspect. type and content, which should not be construed as limiting the present invention.
- the fourth aspect of the present invention provides a method for preparing the plastic parts described in the third aspect, the method comprising:
- the mixing conditions include: the rotating speed is 10-200 rpm, and the time is 3-5 min.
- the mixing conditions include: the rotation speed is 30-150rpm, and the time is 4-5min.
- the extrusion and/or injection molding conditions include: the temperature is 160-240° C., and the pressure-holding cooling time is 1-15 s.
- the extrusion and/or injection molding conditions include: a temperature of 180-230° C., and a pressure-holding cooling time of 5-10 s.
- the purpose of the pressure-holding cooling is to demold the plastic parts.
- the shrinkage is more sufficient, and there is a gap between the plastic parts and the mold, which is easier to demould.
- the extrusion and/or injection molding conditions include: a temperature of 200-220°C.
- the antibacterial masterbatch can not only melt at a sufficient temperature and be uniformly dispersed, but also will not decompose and fail due to excessive temperature, thereby reducing the performance of the plastic product.
- the graft polymer antibacterial plastic composition can select the same plastic raw material and organic matter for graft bonding according to the material of the required plastic parts, and the obtained antibacterial material has good compatibility with the material of the plastic parts, It can endow plastic parts with a long-term and stable antibacterial effect, and there is no problem of excessive precipitation of heavy metals such as silver.
- the fifth aspect of the present invention provides the application of the plastic parts described in the third aspect in the preparation of antibacterial drinking water equipment.
- PE grade PE8916, Guangdong Maoming Petrochemical Co., Ltd.
- Polyhexamethylene monoguanidine hydrochloride grafted PP brand PPNH-1, Shanghai Fuyuan Plastic Technology Co., Ltd., the graft ratio of polyhexamethylene monoguanidine hydrochloride is 20%.
- Polyhexamethylene biguanide nitrate grafted PP brand PPNH-2, Shanghai Fuyuan Plastic Technology Co., Ltd., the graft ratio of polyhexamethylene biguanide nitrate is 12%.
- Polyhexamethylene monoguanidine sulfate grafted PE brand PENH-1, Shanghai Fuyuan Plastic Technology Co., Ltd., the graft ratio of polyhexamethylene monoguanidine sulfate is 15%.
- Polyhexamethylene biguanide hydrochloride grafted PE brand PENH-2, Shanghai Fuyuan Plastic Technology Co., Ltd., the graft ratio of polyhexamethylene biguanide hydrochloride is 8%.
- IONPURE silver-glass antibacterial masterbatch brand IONPURE IPL, Japan Ishizuka Glass Company.
- non-bacterial modified PP plastic parts are used as control parts.
- test methods involved are as follows:
- the antibacterial effect test is carried out with reference to GB/T 31402-2015 plastic surface antibacterial performance test method.
- the calculation method of antibacterial rate is as follows:
- Antibacterial rate (the number of viable bacteria after 24h of the control part - the number of viable bacteria after 24h of the antibacterial part)/the number of viable bacteria after 24h of the control part.
- the plastic parts were prepared according to the following preparation method and the dosage shown in Table 1. Wherein the preparation method is:
- Example 1 The composition of the plastic parts and the specific operation information of Example 1 are listed in Table 1. The remaining examples and comparative examples were carried out by using a process similar to that of Example 1, and the specific conditions are listed in Table 1.
- the comparative example 3 uses IONPURE glass-loaded silver antibacterial masterbatch, and the increase of silver content in water after soaking for 24 hours is much higher than 5ppb, which is not in line with the "Sanitation and Safety Evaluation of Drinking Water Transmission and Distribution Equipment and Protective Materials”. Standard (2001), which will cause heavy metal pollution and unsafe factors to drinking water.
- the antibacterial parts provided by the present invention not only have strong antibacterial effects on Escherichia coli and Staphylococcus aureus, but also the increase of silver content in water after soaking for 24 hours is 0, indicating that there is no silver precipitation and release.
- the graft polymer antibacterial plastic parts provided by the present invention bond the organic antibacterial active ingredients to the polymer molecular chain through chemical bonds. It does not contain silver ions and will not precipitate heavy metals such as silver into the water, and there is no problem of excessive precipitation of heavy metals such as silver.
- the organic antibacterial active ingredient is bonded to the polymer macromolecular chain through chemical bonds, the antibacterial active ingredient still maintains a good antibacterial effect but does not migrate and precipitate, so Overcome the shortcomings of small molecular organic antibacterial agents, such as easy migration and precipitation, poor thermal stability, etc.;
- the graft polymer antibacterial plastic composition provided in some embodiments can select the same plastic raw material and organic matter for graft bonding according to the material of the required plastic parts to obtain antibacterial Masterbatch, the antibacterial masterbatch obtained in this way has better compatibility with the material of plastic parts and longer-lasting and stable antibacterial effect, and there is no problem of excessive precipitation of heavy metals such as silver.
Abstract
La présente invention se rapporte au domaine des matériaux antibactériens pour un équipement d'eau potable, et concerne en particulier une composition de plastique et son utilisation, une pièce en plastique, son procédé de préparation et son utilisation. La composition de plastique contient une matière première plastique et un mélange maître antibactérien dans le rapport pondéral de 100 : 1 à 10. Le mélange maître antibactérien est un polymère greffé avec un composant actif antibactérien, et le taux de greffage du composant actif antibactérien dans le lot maître antibactérien va de 1 à 25 %. Dans la composition de plastique antibactérienne à base de polymère greffé selon la présente invention, du fait que le composant actif antibactérien organique est lié à une chaîne moléculaire de polymère au moyen de liaisons chimiques, le composant actif antibactérien maintient toujours un bon effet antibactérien mais ne migre pas ou ne se précipite pas, et la pièce en plastique formée par la composition de plastique a un effet antibactérien stable et à action prolongée, et ne présente pas le problème de la précipitation de métaux lourds, tels que l'argent, non conforme aux limites.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110387790.3 | 2021-04-09 | ||
| CN202110387790.3A CN113150439A (zh) | 2021-04-09 | 2021-04-09 | 一种塑胶组合物及其应用、塑胶零部件及其制备方法和应用 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2022214057A1 true WO2022214057A1 (fr) | 2022-10-13 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/CN2022/085723 WO2022214057A1 (fr) | 2021-04-09 | 2022-04-08 | Composition de plastique et son utilisation, pièce en plastique, son procédé de préparation et son utilisation |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN113150439A (fr) |
| WO (1) | WO2022214057A1 (fr) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113150439A (zh) * | 2021-04-09 | 2021-07-23 | 佛山市顺德区美的饮水机制造有限公司 | 一种塑胶组合物及其应用、塑胶零部件及其制备方法和应用 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101812160A (zh) * | 2009-02-23 | 2010-08-25 | 上海富元塑胶科技有限公司 | 一种聚烯烃功能化母粒及其制备方法和应用 |
| CN108440761A (zh) * | 2017-02-16 | 2018-08-24 | 中国科学院理化技术研究所 | 一种含有胍基侧链的非释放型高分子抗菌母粒及其制备方法和应用 |
| CN113150439A (zh) * | 2021-04-09 | 2021-07-23 | 佛山市顺德区美的饮水机制造有限公司 | 一种塑胶组合物及其应用、塑胶零部件及其制备方法和应用 |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1112387C (zh) * | 2000-10-26 | 2003-06-25 | 上海塑杰科技有限公司 | 一种聚丙烯专用料及其制备方法和应用 |
| CN1282698C (zh) * | 2002-03-15 | 2006-11-01 | 上海塑杰科技有限公司 | 一种聚烯烃功能化母粒及其制备方法和应用 |
| CN103242618B (zh) * | 2013-05-20 | 2014-05-14 | 江苏惠利隆塑业集团有限公司 | 新型家电用抗菌塑料及其制备方法 |
| CN107725911A (zh) * | 2017-09-26 | 2018-02-23 | 浙江伟星新型建材股份有限公司 | 一种抗菌保温复合管 |
-
2021
- 2021-04-09 CN CN202110387790.3A patent/CN113150439A/zh active Pending
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- 2022-04-08 WO PCT/CN2022/085723 patent/WO2022214057A1/fr unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101812160A (zh) * | 2009-02-23 | 2010-08-25 | 上海富元塑胶科技有限公司 | 一种聚烯烃功能化母粒及其制备方法和应用 |
| CN108440761A (zh) * | 2017-02-16 | 2018-08-24 | 中国科学院理化技术研究所 | 一种含有胍基侧链的非释放型高分子抗菌母粒及其制备方法和应用 |
| CN113150439A (zh) * | 2021-04-09 | 2021-07-23 | 佛山市顺德区美的饮水机制造有限公司 | 一种塑胶组合物及其应用、塑胶零部件及其制备方法和应用 |
Non-Patent Citations (3)
| Title |
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| WANG, YUE ET AL.: "Polypropylene-Grafted Poly(hexamethylene guanidine)/Modified Polyethylene Monofilament and Its Antimicrobial Performance", INTERNATIONAL JOURNAL OF POLYMER SCIENCE, vol. 2020, 10 September 2020 (2020-09-10), XP055787566, DOI: 10.1155/2020/6416230 * |
| WEI DAFU, DING YIFEI, WANG TINGWEN, YANG JUN, GUAN YONG, ZHENG ANNA: "Preparation of nonleaching antimicrobial polypropylene wax and its application in polypropylene", JOURNAL OF APPLIED POLYMER SCIENCE, JOHN WILEY & SONS, INC., US, vol. 134, no. 4, 20 January 2017 (2017-01-20), US , XP055976332, ISSN: 0021-8995, DOI: 10.1002/app.44190 * |
| WEI, CAO ET AL.: "Surface Enrichment and Nonleaching Antimicrobial Performance of Polypropylene Grafted Poly(hexamethylene Guanidine) (PP-g-PHMG) in Poly (ethylene Terephthalate)/PP-g-PHMG", EUROPEAN POLYMER JOURNAL, vol. 118, 1 June 2019 (2019-06-01), XP085775909, DOI: 10.1016/j.eurpolymj.2019.05.062 * |
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| CN113150439A (zh) | 2021-07-23 |
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