CN115746517A - Open-pore silicon dioxide master batch and preparation method and application thereof - Google Patents
Open-pore silicon dioxide master batch and preparation method and application thereof Download PDFInfo
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- CN115746517A CN115746517A CN202211651869.3A CN202211651869A CN115746517A CN 115746517 A CN115746517 A CN 115746517A CN 202211651869 A CN202211651869 A CN 202211651869A CN 115746517 A CN115746517 A CN 115746517A
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- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
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Abstract
The invention provides an open silicon dioxide master batch and a preparation method and application thereof, wherein the raw materials of the open silicon dioxide master batch comprise carrier resin and silicon dioxide in specific parts, and the silicon dioxide comprises gas-phase nano silicon dioxide and/or precipitation-method silicon dioxide; the open-ended silicon dioxide master batch prepared by the polyhydroxy structure contained on the surface of the specific silicon dioxide and the carrier resin is matched, so that the problem that PBAT and PPC are difficult to open in the blend film blowing application process is solved, the synergistic compatibilization effect is achieved, the compatibility of PBAT and PPC materials is improved, and the obtained PBAT/PPC film has excellent processing stability and openness.
Description
Technical Field
The invention belongs to the technical field of silicon dioxide master batches, and particularly relates to an open silicon dioxide master batch as well as a preparation method and application thereof.
Background
PBAT belongs to thermoplastic biodegradable plastic, is a copolymer of butanediol adipate and butanediol terephthalate, has good ductility and elongation at break, thus having good film forming property and being widely applied in the packaging field and the agricultural field.
The propylene oxide and carbon dioxide based copolymer (PPC) is a widely researched carbon dioxide based degradable plastic, the PPC material has the characteristics of excellent normal temperature flexibility, biocompatibility, transparency, barrier property and the like, has huge potential application in the fields of packaging, medical treatment, agricultural film mulching and the like, and has wide market development prospect under the strategic targets of carbon peak, carbon neutralization.
The PBAT/PPC blending material is widely applied to film products at present and has the advantages of good flexibility, controllable barrier property and the like. CN113174124A discloses a PPC and PBAT composite material and a preparation method thereof. The composite material provided by the invention comprises the following raw materials in parts by weight: PPC, PBAT, a polymer modifier, inorganic nano filler and an inorganic nano filler modifier; the polymer modifier is one or more of polymaleic anhydride, succinic anhydride, glyceryl monostearate, acetylated monoglyceride and propylene glycol polyether; the inorganic nano filler modifier is one or more of hexadecyl trimethyl ammonium bromide, gamma-glycidyl ether oxypropyl trimethoxy silane, amino octadecanoic acid and 3-aminopropyl triethoxy silane. The composite material provided by the invention has good mechanical property and crystallization property, lays a good foundation for further expanding the application field of the polypropylene carbonate and poly adipic acid/butylene terephthalate composite material, and has very wide market prospect. However, because the molecular chain end group of the PPC is less, the compatibilization reaction active point is less, the blending compatibility with the PBAT is poor, the blending material is distributed in a sea-island shape, when the addition amount of the PPC is more than 30%, the phenomena of unstable blending extrusion processing, melt fracture and bamboo joint can occur, and in addition, the problems of adhesion and difficult opening are easily caused after the PBAT/PPC blending and film blowing.
Therefore, it is expected to develop an open-pore silica master batch which can improve the compatibility of PBAT and PPC and solve the problem of difficult opening in the blending and film blowing process of PBAT/PPC.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the open silicon dioxide master batch, and the preparation method and the application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides an open-pore silicon dioxide master batch, which comprises the following raw materials in parts by weight:
70 to 85 portions of carrier resin
10 to 25 parts by weight of silicon dioxide
The silica comprises fumed nanosilica and/or precipitated silica.
The open silica master batch provided by the invention comprises a combination of carrier resin and silica, wherein the silica is limited to comprise gas phase nano silica and/or precipitation method silica, and the polyhydroxy structure on the surface of the specific type of silica is utilized to be beneficial to improving the surface reactivity of a matrix phase and a disperse phase, so that when the open silica master batch is applied to the preparation of a PBAT/PPC composite material, the compatibility of PBAT and PPC is promoted, and meanwhile, the problem that a blend of PBAT and PPC is difficult to open in the film blowing application process can be solved, and further, the PBAT/PPC film prepared by using the open silica master batch provided by the invention as one of raw materials has excellent mechanical properties and also has excellent processing stability and opening property.
Wherein the carrier resin may be 72 parts by weight, 74 parts by weight, 76 parts by weight, 78 parts by weight, 80 parts by weight, 82 parts by weight, 84 parts by weight, or the like.
The silica may be 12 parts by weight, 14 parts by weight, 16 parts by weight, 18 parts by weight, 20 parts by weight, 22 parts by weight, 24 parts by weight, or the like.
Preferably, the fumed nanosilica has a particle size of 10 to 20nm, e.g. 11nm, 12nm, 13nm, 14nm, 15nm, 16nm, 17nm, 18nm or 19nm, etc.
Preferably, the fumed silica comprises hydrophobic fumed silica and/or hydrophilic fumed silica.
Preferably, the precipitated silica has a particle size of 10 to 40 μm, for example 15 μm, 20 μm, 25 μm, 30 μm or 35 μm.
Preferably, the precipitated fumed silica comprises a hydrophobic type precipitated fumed silica and/or a hydrophilic type precipitated silica.
Preferably, the carrier resin comprises a biodegradable resin.
Preferably, the biodegradable resin includes any one of or a combination of at least two of polylactic acid (PLA), polybutylene adipate-terephthalate (PBAT), polybutylene succinate (PBS), or polypropylene carbonate (PPC).
Preferably, the raw material of the open-pore silica master batch further comprises a coupling agent and/or a lubricant.
Preferably, the content of the coupling agent in the raw material of the open-pore silica master batch is 0 to 2 parts by weight and is not equal to 0, for example, 0.2 part by weight, 0.4 part by weight, 0.6 part by weight, 0.8 part by weight, 1 part by weight, 1.2 parts by weight, 1.4 parts by weight, 1.6 parts by weight, or 1.8 parts by weight.
Preferably, the coupling agent comprises any one of a silane coupling agent, an aluminate coupling agent, a titanate coupling agent or a borate coupling agent or a combination of at least two thereof.
Preferably, the content of the lubricant in the raw material of the open-pore silica master batch is 0 to 2 parts by weight and is not equal to 0, for example, 0.2 part by weight, 0.4 part by weight, 0.6 part by weight, 0.8 part by weight, 1 part by weight, 1.2 parts by weight, 1.4 parts by weight, 1.6 parts by weight, or 1.8 parts by weight.
Preferably, the lubricant comprises any one of or a combination of at least two of vinyl bis stearamide, polyethylene wax, oxidized polyethylene wax, montan wax, erucamide, oleamide, stearic acid, calcium stearate, or magnesium stearate.
In a second aspect, the present invention provides a method for preparing the open-pore silica masterbatch according to the first aspect, wherein the method comprises: and extruding and granulating the carrier resin, the silicon dioxide, the optional coupling agent and the optional lubricant to obtain the open-pore silicon dioxide master batch.
Preferably, the extrusion granulation is performed in a twin screw extruder.
Preferably, the temperature of the extrusion granulation is 140 to 170 ℃, for example 145 ℃, 150 ℃, 155 ℃, 160 ℃, 165 ℃ or 170 ℃.
Preferably, the twin-screw extruder has a rotation speed of 150 to 300rpm, such as 160rpm, 180rpm, 200rpm, 220rpm, 240rpm, 260rpm, 280rpm, or the like.
Preferably, the preparation method specifically comprises: and (2) blanking the carrier resin from a main feeding port of a double-screw extruder, uniformly stirring and mixing the silicon dioxide, the optional coupling agent and the optional lubricating agent, blanking from a side feeding port of the double-screw extruder, extruding at the main machine rotating speed of the double-screw extruder of 150-300 rpm and the extruder temperature of 140-170 ℃, and carrying out air cooling and granulating to obtain the open silicon dioxide master batch.
In a third aspect, the invention provides a PBAT/PPC film, wherein the raw material for preparing the PBAT/PPC film comprises a combination of the open-pore silica master batch, the PBAT, and the PPC.
Preferably, the raw materials for preparing the PBAT/PPC film comprise the following components in parts by weight:
60 to 80 portions of PBAT
10 to 30 portions of PPC
7-9 parts of open-ended silica master batch.
Wherein the PBAT may be 62, 64, 66, 68, 70, 72, 74, 76, 78, etc. parts by weight.
The PPC may be 12, 14, 16, 18, 20, 22, 24, 26, or 28 parts by weight, etc.
The open-pore silica master batch may be 7.2 parts by weight, 7.4 parts by weight, 7.6 parts by weight, 7.8 parts by weight, 8 parts by weight, 8.2 parts by weight, 8.4 parts by weight, 8.6 parts by weight, 8.8 parts by weight, or the like.
Preferably, the raw material for preparing the PBAT/PPC film also comprises a processing aid.
In a fourth aspect, the invention provides a use of the PBAT/PPC film according to the third aspect in packaging materials, medical materials or agricultural films.
Compared with the prior art, the invention has the following beneficial effects:
(1) The carrier resin selected in the open silicon dioxide master batch provided by the invention can effectively improve the distribution of silicon dioxide in a matrix phase or a disperse phase, and the surfaces of the selected gas phase nano silicon dioxide and/or precipitation method silicon dioxide contain polyhydroxy structures, so that the surface reaction active points of the matrix phase or the disperse phase can be improved, and the compatibility of PBAT/PPC two phases is improved.
(2) The preparation method of the open silicon dioxide master batch provided by the invention is simple to operate, environment-friendly and beneficial to industrial production.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitation of the present invention.
The information on the raw materials involved in the detailed description is as follows:
PBAT: is from Zhejiang Huafeng environmental protection materials Co., ltd, the mark is HF101, and the melt index is 3-5 g/10min;
PPC: is from Zhejiang Huafeng environmental protection materials Co., ltd, and has a melt index of 1-5 g/10min;
coupling agent: titanate coupling agent TCA, available from nanjing energy de new materials technologies ltd;
lubricant: vinyl bis stearamide, available from usa dragon sand;
hydrophobic fumed nano silica: the average grain diameter is 16nm, and the product is purchased from Germany;
hydrophilic type gas phase nano silicon dioxide: the average grain diameter is 12nm, and the product is purchased from Germany;
hydrophobic precipitated silica: the average particle size is 6 μm, and the product is purchased from Shanghai West Union chemical industry;
hydrophilic precipitated silica: the average grain diameter is 4.5 mu m, and the product is purchased from Shanghai West Union chemical industry;
antioxidant 1010 and antioxidant 168 (parts by weight 1:1), available from novice chemistry;
epoxy chain extender: epoxy chain extender 4400, available from BASF.
Examples 1 to 12
An open silicon dioxide master batch comprises the raw materials of which the components are shown in the table 1, and the dosage unit of each component is 'weight part';
TABLE 1
The preparation method of the open-pore silica masterbatch provided in embodiments 1 to 12 includes: and (2) blanking the carrier resin from a main feeding port of a double-screw extruder, uniformly stirring and mixing the silicon dioxide, the coupling agent and the lubricant, then blanking from a side feeding port of the double-screw extruder, extruding at the main machine rotating speed of the double-screw extruder of 200rpm and the extruder temperature of 150 ℃, and air-cooling and granulating to obtain the open-ended silicon dioxide master batch.
Comparative example 1
A master batch which is different from the master batch of the embodiment 1 only in that the addition amount of PBAT is 95 parts by weight, hydrophobic fumed nano silica is not added, and other components, the use amount and the preparation method are the same as those of the master batch of the embodiment 1.
Comparative example 2
A master batch which is different from the master batch of the example 5 only in that the addition amount of the PPC is 95 parts by weight, the hydrophobic fumed nano silica is not added, and other components, the use amount and the preparation method are the same as those of the master batch of the example 5.
Application examples 1 to 12
The PBCT/PPC film comprises the raw materials of which the components are shown in Table 2, wherein the open-ended silica master batches provided in examples 1 to 12 are respectively added in application examples 1 to 12, and the dosage unit of each component is 'part by weight';
TABLE 2
The preparation method of the PBAT/PPC film provided in application examples 1 to 12 comprises the following steps: uniformly mixing the open silicon dioxide master batch, PBAT, PPC, an antioxidant, vinyl distearamide and an epoxy chain extender, then extruding by using a double-screw extruder, wherein the extrusion temperature is 160 ℃, air-cooling and granulating, and performing film blowing molding in a main control temperature zone within a temperature range of 135 ℃ by using a film blowing machine, wherein the film thickness is 30 mu m, thus obtaining the PBAT/PPC film.
Comparative application examples 1 to 2
A PBAT/PPC film, which is different from application example 1 only in that the open silica master batch obtained in comparative examples 1 to 2 was used instead of the open silica master batch provided in example 1, and the other components, the amounts, and the preparation methods were the same as those of application example 1.
And (3) performance testing:
(1) Tensile strength and elongation at break: testing on a universal testing machine according to a testing method provided by the standard GB/1040.2-2006, wherein the tensile speed is 500mm/min;
(2) Opening property: two PBAT/PPC films are overlapped and then rubbed with fingers, so that the PBAT/PPC films are very easy to be rubbed and opened to form 'good', the PBAT/PPC films are easier to be rubbed and opened to form 'medium', and the PBAT/PPC films are not easy to be rubbed and opened to form 'poor';
(3) And (3) processing stability: and observing whether the material strips in the double-screw extrusion process are uniform or not, and whether the production is discontinuous due to the discontinuous phenomena of bamboo joint and the like.
The PBCT/PPC films provided in application examples 1 to 12 and comparative application examples 1 to 2 were tested according to the above test method, and the test results are shown in table 3:
TABLE 3
As can be seen from the data in table 3:
the PBCT/PPC films provided in application examples 1 to 12 were excellent in the openability and the processing stability, and had high tensile strength (tensile strength in the machine direction of 35 to 42 MPa) and high elongation at break (elongation at break in the machine direction of 372 to 462%).
Comparing the data of application example 1 with the data of application example 1, and application example 5 with the data of application example 5 shows that the PBCT/PPC film obtained without adding the open-ended silica master batch has poor mechanical properties, good open-ended performance and processing stability.
Comparing the data of application example 1 and application examples 11 and 12, it can also be seen that the addition of lubricant and coupling agent also helps to improve the mechanical properties of the PBCT/PPC film.
The applicant states that the present invention is described by the above embodiments, but the present invention is not limited to the above embodiments, i.e. it does not mean that the present invention is implemented only by relying on the above embodiments. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The open silicon dioxide master batch is characterized by comprising the following raw materials in parts by weight:
70 to 85 parts by weight of carrier resin
10 to 25 parts by weight of silica
The silica comprises fumed nanosilica and/or precipitated silica.
2. The open silica masterbatch according to claim 1, wherein the fumed silica has a particle size of 10 to 20nm;
preferably, the fumed nano-silica comprises hydrophobic fumed nano-silica and/or hydrophilic fumed nano-silica;
preferably, the particle size of the precipitated silica is 10 to 40 μm;
preferably, the precipitated fumed silica comprises a hydrophobic type precipitated fumed silica and/or a hydrophilic type precipitated silica.
3. The open silica masterbatch according to claim 1 or 2, wherein the carrier resin comprises a biodegradable resin;
preferably, the biodegradable resin includes any one of or a combination of at least two of polylactic acid, polybutylene adipate-terephthalate, polybutylene succinate, or polypropylene carbonate.
4. The open silica masterbatch according to any one of claims 1 to 3, wherein the raw material of the open silica masterbatch further comprises a coupling agent and/or a lubricant;
preferably, the content of the coupling agent in the raw material of the open-pore silicon dioxide master batch is 0-2 parts by weight and is not equal to 0;
preferably, the coupling agent comprises any one or a combination of at least two of a silane coupling agent, an aluminate coupling agent, a titanate coupling agent or a borate coupling agent;
preferably, the content of the lubricant in the raw material of the open-pore silicon dioxide master batch is 0-2 parts by weight and is not equal to 0;
preferably, the lubricant comprises any one of or a combination of at least two of vinyl bis stearamide, polyethylene wax, oxidized polyethylene wax, montan wax, erucamide, oleamide, stearic acid, calcium stearate, or magnesium stearate.
5. A method of preparing the open-celled silica masterbatch of any one of claims 1 to 4, wherein the method comprises: and extruding and granulating the carrier resin, the silicon dioxide, the optional coupling agent and the optional lubricant to obtain the open-pore silicon dioxide master batch.
6. The method of claim 5, wherein the extrusion granulation is performed in a twin-screw extruder;
preferably, the temperature of the extrusion granulation is 140-170 ℃;
preferably, the rotation speed of the twin-screw extruder is 150 to 300rpm.
7. The preparation method according to claim 5 or 6, characterized in that the preparation method specifically comprises: and (2) blanking the carrier resin from a main feeding port of a double-screw extruder, uniformly stirring and mixing the silicon dioxide, the optional coupling agent and the optional lubricating agent, blanking from a side feeding port of the double-screw extruder, extruding at the main machine rotating speed of the double-screw extruder of 150-300 rpm and the extruder temperature of 140-170 ℃, and carrying out air cooling and granulating to obtain the open silicon dioxide master batch.
8. A PBAT/PPC film, characterized in that the raw material for preparing the PBAT/PPC film comprises the open-ended silica masterbatch of any one of claims 1 to 4, PBAT and PPC.
9. The PBAT/PPC film according to claim 8, wherein the raw materials for preparing the PBAT/PPC film comprise the following components in parts by weight:
60 to 80 portions of PBAT
10 to 30 portions of PPC
7-9 parts of open-ended silicon dioxide master batch;
preferably, the raw material for preparing the PBAT/PPC film also comprises a processing aid.
10. Use of the PBAT/PPC film of claim 9 in packaging materials, medical materials or agricultural films.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103756270A (en) * | 2013-12-31 | 2014-04-30 | 山东农业大学 | Full biodegrade mulch master batch as well as preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103756270A (en) * | 2013-12-31 | 2014-04-30 | 山东农业大学 | Full biodegrade mulch master batch as well as preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 郑水林 等: "粉体表面改性", vol. 4, 中国建材工业出版社, pages: 73 - 91 * |
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