WO2018099222A1 - Biodegradable additive and polyethylene film material containing same - Google Patents

Biodegradable additive and polyethylene film material containing same Download PDF

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Publication number
WO2018099222A1
WO2018099222A1 PCT/CN2017/108040 CN2017108040W WO2018099222A1 WO 2018099222 A1 WO2018099222 A1 WO 2018099222A1 CN 2017108040 W CN2017108040 W CN 2017108040W WO 2018099222 A1 WO2018099222 A1 WO 2018099222A1
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Prior art keywords
copper
mass
temperature
copper powder
additive
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PCT/CN2017/108040
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French (fr)
Chinese (zh)
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陆海荣
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苏州天兼新材料科技有限公司
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Publication of WO2018099222A1 publication Critical patent/WO2018099222A1/en

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0856—Iron
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/06—Biodegradable
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/066—LDPE (radical process)

Definitions

  • the present invention relates to a biodegradable additive, and more particularly to a copper-containing biodegradable additive capable of imparting biodegradability to a conventional non-biodegradable plastic article, and to a plastic article containing the additive, particularly Additive polyethylene film material.
  • Plastic products are widely used in food packaging because of their low price, good durability and good antibacterial properties.
  • plastic products such as plastic convenience bags and plastic films
  • the problem of "white pollution” has become increasingly prominent. This is due to the inherent life of the plastic product (from the finished product to the complete natural decomposition) is much longer than its service life.
  • the inherent durability of the plastic causes it to exist in nature for a long time without being treated.
  • the methods for solving this problem mainly include deep burial and incineration. Deeply occupying cultivated land, polluting groundwater, changing soil structure, affecting normal plant growth, and high cost; incineration is currently the most widely used white pollution control method, fast and low cost, but the significant disadvantage is that it brings additional Air Pollution.
  • biodegradable plastics Since biodegradable plastics can be naturally degraded under the influence of natural conditions such as ultraviolet light, rain water, etc., and no pollutants are generated after degradation, this problem can be fundamentally solved.
  • Biodegradable plastics which have been developed include polylactic acid, polybutylene succinate, polybutylene succinate, polybutylene terephthalate, and the like.
  • biodegradable plastics have the following advantages: (1) reduced volume after degradation, can save land occupation land and save land resources; (2) reduce incineration of harmful gases without incineration; (3) can be made into compost to return to nature .
  • the existing biodegradable plastics have the following drawbacks: (1) the cost is high, and accordingly, the price is 2 to 6 times higher than that of ordinary plastics; (2) the physical and mechanical properties are poor. Tensile strength, elongation at break, bursting and tearing strength, light transparency, wet strength, etc. are not met. The above two points have seriously affected the biodegradable plastic products. Use range.
  • the following topics have been proposed: the development of a biodegradable additive by which the inherent life and service life of various plastic products, including ordinary plastics, are effectively combined to impart conventional biodegradability.
  • the plastic obtains the degradation property after use, and ensures that the plastic product to which the biodegradation additive is added is not affected during use, and can be quickly decomposed after use to avoid the occurrence of white pollution.
  • an object of the present invention is to provide a biodegradable additive for imparting biodegradability to a conventional plastic article, a method for preparing the biodegradable additive, and a plastic article prepared by using the biodegradable additive, in particular It is a polyethylene film product.
  • a copper-containing biodegradation additive comprising: 2 to 8 mass% of copper powder, 0.01% to 0.30 mass% of a silane coupling agent, and a balance Low density polyethylene.
  • a copper-containing biodegradation additive according to an embodiment of the present invention wherein the copper powder is copper powder having a particle diameter of 2 ⁇ m or less, and the amount is 5% by mass.
  • a copper-containing biodegradation additive according to an embodiment of the present invention wherein the silane coupling agent is 3-aminopropyltriethoxysilane.
  • a method for preparing the above copper-containing biodegradable additive comprising the steps of: Step 1: weighing the components in proportion; and step 2: coupling the copper powder with silane The surface treatment is carried out; Step 3: the copper powder and the polyethylene after the surface treatment of the second step are placed in a high-speed high-shear mixing device for stirring and mixing; Step 4: the twin-screw granulator will pass the third step The uniformly mixed material is made into granules.
  • a method of preparing the above copper-containing biodegradation additive according to a specific embodiment of the present invention wherein in the third step, the rotation speed of the high-speed high-shear mixing device is set to 750 rpm, and the temperature is set to 85 ° C.
  • the mixing time is set to 10 minutes.
  • a method for preparing the above copper-containing biodegradable additive wherein, in the fourth step, setting a temperature of the second zone to a maximum temperature, that is, 180 ° C, maintaining the set temperature, so that The temperature in one zone is 10 °C lower than that in the second zone, so that the temperature in the third zone and the fourth zone is the same as that in the second zone. From the five zones until the nose gradually decreases according to the gradient, the temperature of the head is kept constant (in the range of 130-150 °C).
  • a plastic article comprising the above copper-containing biodegradation additive in an amount of from 1 to 3% by mass.
  • a polyethylene film product comprising the above copper-containing biodegradation additive in an amount of from 1 to 3% by mass.
  • the biodegradation additive of the invention can effectively combine the intrinsic life and the service life of various plastic products including common plastics, and not only imparts degradation performance to traditional non-biodegradable plastics after use, but also ensures The plastic product to which the biodegradation additive is added is not affected by the performance during use, and can be quickly decomposed after use to avoid the occurrence of white pollution.
  • the present invention also provides a plastic article such as a polyethylene film article capable of rapid biodegradation, which contains the biodegradation additive without causing white pollution problems.
  • the biodegradation additive of the present invention uses copper powder, a silane coupling agent, and a low density polyethylene as raw materials.
  • the copper powder is a copper powder having a particle diameter of 2 ⁇ m or less, the amount thereof is 2 to 8% by mass, and the silane coupling agent is 3-aminopropyltriethoxysilane, and the amount thereof is 0.01 to 0.30% by mass, and the balance is It is low density polyethylene (LDPE).
  • LDPE low density polyethylene
  • the amount of the copper powder is 5% by mass
  • the amount of the silane coupling agent is 0.01 to 0.30% by mass
  • the low density polyethylene is a low density polyethylene having a lower melting point. It is 94.7 to 94.99% by mass.
  • the copper-containing biodegradation additive of the present invention is prepared by the following steps:
  • Step 1 Weigh each component within the mass fraction range as described above;
  • Step 2 Surface treatment of the copper powder with a silane coupling agent;
  • Step 3 Place the surface treated copper powder and polyethylene in the second step
  • the high-speed high-shear mixing equipment is mixed and stirred, wherein the rotation speed of the equipment is set to 750 rpm, the temperature is set to 85 ° C, and the mixing time is set to 10 minutes;
  • Step 4 uniformly mixing the high-speed high-shear mixing equipment in the third step
  • the resulting material is fed into a twin-screw granulator to produce particles having the same particle size as the polyethylene plastic particles, i.e., as a biodegradable additive.
  • the length-to-diameter ratio of the twin-screw granulator is 40, and the temperature control is very important.
  • the temperature in the second zone is set to the highest temperature, that is, 180 °C, and the set temperature is maintained, so that the temperature of one zone is 5-15 °C lower than that of the second zone.
  • the temperature in the three zones and the four zones is substantially the same as that of the second zone, and the temperature of the three zones is gradually decreased from the five zones until the machine head is gradually lowered according to the gradient temperature, and the temperature of the head is kept constant (in the range of 130 to 150 ° C).
  • the biodegradation additive 2 was prepared in the same manner as in Example 1 except for the difference in the ingredients shown in the above table (as shown in Table 2).
  • the biodegradation additive 3 was prepared in the same manner as in Example 1 except for the difference in the ingredients shown in the above table (as shown in Table 3).
  • the biodegradation additive 4 was prepared in the same manner as in Example 1 except for the difference in the ingredients shown in the above table (as shown in Table 4).
  • the biodegradation additive 5 was prepared in the same manner as in Example 1 except for the difference in the ingredients shown in the above table (as shown in Table 5).
  • the biodegradable additive prepared by the above steps can be directly added to a conventional plastic product in a proportion of 1-3 mass%, for example, added to a polyethylene plastic to impart biodegradability, accelerate the decomposition process, and make the conventional plastic product an environment.
  • Degradable plastic products This technology is particularly suitable for the production of environmentally friendly packaging materials, disposable plastic products, agricultural disposable film (especially film products) and other film plastic products. These products undergo an oxidation reaction in a natural environment, causing an increase in carboxylic acid groups to impart biodegradability to non-biodegradable plastic articles. These environmentally friendly plastic products eventually degrade into carbon dioxide, water and humus. The method of use thereof will be described below with reference to the embodiments, but the invention is not limited thereto.
  • the above biodegradable additives 1 to 5 are sufficiently mixed with 2% by mass, low density polyethylene (LDPE) 88% by mass, and linear low density polyethylene (LLDPE) 10% by mass, and then added to a single screw extruder (extruder).
  • LDPE low density polyethylene
  • LLDPE linear low density polyethylene
  • the aspect ratio of 20 to 30) was blown into a film having a thickness of 25 ⁇ m, and the polyethylene films prepared by the above biodegradable additives 1 to 5 were respectively named as polyethylene films A to E.
  • the prepared polyethylene films A to E were respectively irradiated with ultraviolet light (the ultraviolet light source is an ultraviolet lamp emitting light of 340 nm wavelength, the intensity is 0.78 ⁇ 0.02 W/m 2 ⁇ mm) and The thermal oxidation treatment was carried out to measure the longitudinal elongation of the polyethylene film before and after the ultraviolet light irradiation and heating, and the results are shown in Table 6.
  • the ultraviolet light source is an ultraviolet lamp emitting light of 340 nm wavelength, the intensity is 0.78 ⁇ 0.02 W/m 2 ⁇ mm
  • the thermal oxidation treatment was carried out to measure the longitudinal elongation of the polyethylene film before and after the ultraviolet light irradiation and heating, and the results are shown in Table 6.
  • the tensile strength of the polyethylene film of the present invention is significantly improved relative to the reference film, and the strength of the polyethylene film containing the biodegradable additive of the present invention is higher than that of the polyethylene film without the biodegradation additive. 40% or more.

Abstract

The present invention relates to a copper-containing biodegradable additive, consisting of the following components: 2-8% by mass of copper powder, 0.01%-0.30% by mass of a silane coupling agent, and the balance of low density polyethylene. The present invention also relates to a method for preparing the copper-containing biodegradable additive and a plastic product containing 1-3% by mass of the copper-containing biodegradable additive, particularly a polyethylene film product, which can be biodegraded rapidly and thoroughly without producing white pollution.

Description

一种生物降解添加剂及含有该添加剂的聚乙烯薄膜材料Biodegradation additive and polyethylene film material containing the same 技术领域Technical field
本发明涉及一种生物降解添加剂，特别涉及一种含铜的生物降解添加剂，其能够赋予常规的非生物降解的塑料制品生物降解性能，本发明还涉及含有该添加剂的塑料制品，特别是含有该添加剂的聚乙烯薄膜材料。The present invention relates to a biodegradable additive, and more particularly to a copper-containing biodegradable additive capable of imparting biodegradability to a conventional non-biodegradable plastic article, and to a plastic article containing the additive, particularly Additive polyethylene film material.
背景技术Background technique
塑料制品因价廉物美，经久耐用且抗菌性能好，广泛用于食品包装领域。然而，随着以塑料方便袋、塑料薄膜等塑料制品的广泛使用，“白色污染”问题也日益凸显。这是由于塑料制品的内在寿命(从制得成品到完全自然分解)远远长于其使用寿命。塑料内在的耐久性，导致如不对其进行处理则长久存在于自然界并越积越多。目前解决这一问题的方法主要有深埋和焚烧等。深埋占用耕地，污染地下水原，改变土壤结构，影响植物正常生长，且成本较高；焚烧是目前使用最为广泛的白色污染治理方法，速度快，成本低，但显著缺点是带来了额外的大气污染。Plastic products are widely used in food packaging because of their low price, good durability and good antibacterial properties. However, with the widespread use of plastic products such as plastic convenience bags and plastic films, the problem of "white pollution" has become increasingly prominent. This is due to the inherent life of the plastic product (from the finished product to the complete natural decomposition) is much longer than its service life. The inherent durability of the plastic causes it to exist in nature for a long time without being treated. At present, the methods for solving this problem mainly include deep burial and incineration. Deeply occupying cultivated land, polluting groundwater, changing soil structure, affecting normal plant growth, and high cost; incineration is currently the most widely used white pollution control method, fast and low cost, but the significant disadvantage is that it brings additional Air Pollution.
已经提出了可生物降解塑料的技术方案，由于可生物降解塑料能够在自然条件如紫外光、雨水等的影响下自然降解，且降解之后不产生污染物，因此能够从根本上解决这一问题。已经开发的可生物降解塑料有聚乳酸、聚丁二酸丁二醇酯、聚丁二酸己二酸丁二醇酯、聚己二酸对苯二甲酸丁二醇酯等。虽然生物可降解塑料具有如下优点：(1)降解后体积减小，能节省占用填埋场土地，节约土地资源；(2)不用焚烧，减少有害气体排放；(3)可制成堆肥回归自然。但是，现有的可生物降解的塑料存在如下缺陷：(1)成本偏高，相应地，其价格也比普通塑料高2～6倍；(2)物理力学性能差。其拉伸强度、断裂伸长率、顶破和撕裂强度、光透明性、湿强度等都达不到应用的要求。以上两点严重影响了可生物降解塑料制品的应 用范围。A technical solution for biodegradable plastics has been proposed. Since biodegradable plastics can be naturally degraded under the influence of natural conditions such as ultraviolet light, rain water, etc., and no pollutants are generated after degradation, this problem can be fundamentally solved. Biodegradable plastics which have been developed include polylactic acid, polybutylene succinate, polybutylene succinate, polybutylene terephthalate, and the like. Although biodegradable plastics have the following advantages: (1) reduced volume after degradation, can save land occupation land and save land resources; (2) reduce incineration of harmful gases without incineration; (3) can be made into compost to return to nature . However, the existing biodegradable plastics have the following drawbacks: (1) the cost is high, and accordingly, the price is 2 to 6 times higher than that of ordinary plastics; (2) the physical and mechanical properties are poor. Tensile strength, elongation at break, bursting and tearing strength, light transparency, wet strength, etc. are not met. The above two points have seriously affected the biodegradable plastic products. Use range.
鉴于此，提出了以下课题：开发一种生物降解添加剂，通过其使用，使包括普通塑料在内的各种塑料制品的内在寿命和使用寿命有效地结合起来，既赋予传统的不能够生物降解的塑料在使用后获得降解性能，又保证添加该生物降解添加剂的塑料制品在使用期间使用性能不受影响，使用结束之后能够迅速分解，避免白色污染的出现。In view of this, the following topics have been proposed: the development of a biodegradable additive by which the inherent life and service life of various plastic products, including ordinary plastics, are effectively combined to impart conventional biodegradability. The plastic obtains the degradation property after use, and ensures that the plastic product to which the biodegradation additive is added is not affected during use, and can be quickly decomposed after use to avoid the occurrence of white pollution.
发明内容Summary of the invention
针对上述问题，本发明的目的是提供一种用于赋予传统的塑料制品以生物降解性能的生物降解添加剂、一种制备该生物降解添加剂的方法、及采用该生物降解添加剂制备的塑料制品，特别是聚乙烯薄膜制品。In view of the above problems, an object of the present invention is to provide a biodegradable additive for imparting biodegradability to a conventional plastic article, a method for preparing the biodegradable additive, and a plastic article prepared by using the biodegradable additive, in particular It is a polyethylene film product.
为达到上述目的，本发明采用如下技术方案：In order to achieve the above object, the present invention adopts the following technical solutions:
根据本发明的一个具体实施方式，提供了一种含铜的生物降解添加剂，其由以下组分组成：2～8质量％的铜粉、0.01％～0.30质量％的硅烷偶联剂、余量的低密度聚乙烯。According to a specific embodiment of the present invention, there is provided a copper-containing biodegradation additive comprising: 2 to 8 mass% of copper powder, 0.01% to 0.30 mass% of a silane coupling agent, and a balance Low density polyethylene.
根据本发明的一个实施例的含铜的生物降解添加剂，其中，所述铜粉为粒径2微米以下的铜粉，用量为5质量％。A copper-containing biodegradation additive according to an embodiment of the present invention, wherein the copper powder is copper powder having a particle diameter of 2 μm or less, and the amount is 5% by mass.
根据本发明的一个实施例的含铜的生物降解添加剂，其中，所述硅烷偶联剂为3-氨丙基三乙氧基硅烷。A copper-containing biodegradation additive according to an embodiment of the present invention, wherein the silane coupling agent is 3-aminopropyltriethoxysilane.
根据本发明的一个具体实施方式，提供了一种制备上述含铜的生物降解添加剂的方法，其包含以下步骤：步骤一：按比例称量各组分；步骤二：将铜粉用硅烷偶联剂进行表面处理；步骤三：将经过所述步骤二的表面处理之后的铜粉和聚乙烯放入高速高剪切混料设备进行搅拌混合；步骤四：以双螺杆造粒机将通过步骤三均匀混合后的物料制成颗粒。According to a specific embodiment of the present invention, there is provided a method for preparing the above copper-containing biodegradable additive, comprising the steps of: Step 1: weighing the components in proportion; and step 2: coupling the copper powder with silane The surface treatment is carried out; Step 3: the copper powder and the polyethylene after the surface treatment of the second step are placed in a high-speed high-shear mixing device for stirring and mixing; Step 4: the twin-screw granulator will pass the third step The uniformly mixed material is made into granules.
根据本发明的一个具体实施例的制备上述含铜的生物降解添加剂的方法，其中，在所述步骤三中，将所述高速高剪切混料设备的转速设为750rpm，温度设为85℃，混合时间设为10分钟。A method of preparing the above copper-containing biodegradation additive according to a specific embodiment of the present invention, wherein in the third step, the rotation speed of the high-speed high-shear mixing device is set to 750 rpm, and the temperature is set to 85 ° C. The mixing time is set to 10 minutes.
根据本发明的一个具体实施例的制备上述含铜的生物降解添加剂的 方法，其中，在所述步骤四中，所述双螺杆造粒机的长径比为40。Preparation of the above copper-containing biodegradable additive according to a specific embodiment of the present invention The method wherein, in the step (4), the twin-screw granulator has an aspect ratio of 40.
根据本发明的一个具体实施例的制备上述含铜的生物降解添加剂的方法，其中，在所述步骤四中，设定二区温度为最高温度，即180℃，保持该设定的温度，使一区比二区温度低10℃，使三区、四区温度与二区相同，从五区开始直至机头按梯度逐渐降低，保持机头温度为恒定温度(130～150℃范围内)。According to a specific embodiment of the present invention, a method for preparing the above copper-containing biodegradable additive, wherein, in the fourth step, setting a temperature of the second zone to a maximum temperature, that is, 180 ° C, maintaining the set temperature, so that The temperature in one zone is 10 °C lower than that in the second zone, so that the temperature in the third zone and the fourth zone is the same as that in the second zone. From the five zones until the nose gradually decreases according to the gradient, the temperature of the head is kept constant (in the range of 130-150 °C).
根据本发明的一个具体实施方式，提供了一种塑料制品，其含有上述含铜的生物降解添加剂1～3质量％。According to a specific embodiment of the present invention, there is provided a plastic article comprising the above copper-containing biodegradation additive in an amount of from 1 to 3% by mass.
根据本发明的一个具体实施方式，提供了一种聚乙烯薄膜制品，其含有上述含铜的生物降解添加剂1～3质量％。According to a specific embodiment of the present invention, there is provided a polyethylene film product comprising the above copper-containing biodegradation additive in an amount of from 1 to 3% by mass.
本发明的生物降解添加剂，能够使使包括普通塑料在内的各种塑料制品的内在寿命和使用寿命有效地结合起来，既赋予传统的不能够生物降解的塑料在使用后获得降解性能，又保证添加该生物降解添加剂的塑料制品在使用期间使用性能不受影响，使用结束之后能够迅速分解，避免白色污染的出现。特别地，本发明还提供了能够迅速生物降解的塑料制品如聚乙烯薄膜制品，其含有该生物降解添加剂，不会引发白色污染问题。The biodegradation additive of the invention can effectively combine the intrinsic life and the service life of various plastic products including common plastics, and not only imparts degradation performance to traditional non-biodegradable plastics after use, but also ensures The plastic product to which the biodegradation additive is added is not affected by the performance during use, and can be quickly decomposed after use to avoid the occurrence of white pollution. In particular, the present invention also provides a plastic article such as a polyethylene film article capable of rapid biodegradation, which contains the biodegradation additive without causing white pollution problems.
具体实施方式detailed description
为了使本发明的目的、技术方案及优点更加清楚明白，下面结合实施例对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅用以解释本发明，并不用于限定本发明。In order to make the objects, technical solutions and advantages of the present invention more comprehensible, the present invention will be further described in detail below in conjunction with the embodiments. It is understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
生物降解添加剂的制备Preparation of biodegradable additives
本发明的生物降解添加剂以铜粉、硅烷偶联剂、低密度聚乙烯为原料。其中，铜粉为粒径2微米以下的铜粉，其用量为2～8质量％，硅烷偶联剂为3-氨丙基三乙氧基硅烷，其用量为0.01～0.30质量％，余量为低密度聚乙烯(LDPE)。The biodegradation additive of the present invention uses copper powder, a silane coupling agent, and a low density polyethylene as raw materials. Wherein, the copper powder is a copper powder having a particle diameter of 2 μm or less, the amount thereof is 2 to 8% by mass, and the silane coupling agent is 3-aminopropyltriethoxysilane, and the amount thereof is 0.01 to 0.30% by mass, and the balance is It is low density polyethylene (LDPE).
在一个进一步的实施例中，铜粉的用量为5质量％，硅烷偶联剂用量为0.01～0.30质量％，低密度聚乙烯为熔点较低的低密度聚乙烯，其用量 为94.7～94.99质量％。In a further embodiment, the amount of the copper powder is 5% by mass, the amount of the silane coupling agent is 0.01 to 0.30% by mass, and the low density polyethylene is a low density polyethylene having a lower melting point. It is 94.7 to 94.99% by mass.
在一个进一步的实施例中，本发明的含铜的生物降解添加剂由如下步骤制备而成：In a further embodiment, the copper-containing biodegradation additive of the present invention is prepared by the following steps:
步骤一：称量如上所述质量分数范围内的各组分；步骤二：用硅烷偶联剂对铜粉进行表面处理；步骤三：将步骤二中经表面处理的铜粉与聚乙烯放入高速高剪切混料设备进行混合搅拌，其中将设备的转速设为750rpm，温度设为85℃，混合时间设为10分钟；步骤四：将步骤三中通过高速高剪切混料设备均匀混合后的物料送入双螺杆造粒机内制成和聚乙烯塑料粒子具有相同颗粒大小的粒子，即，制成生物降解添加剂。其中双螺杆造粒机的长径比为40，其温度控制非常重要，设定二区温度是最高温度即180℃，保持设定的温度，使一区比二区温度低5～15℃，优选10℃左右，使三区、四区温度与二区基本相同，从五区开始直至机头按梯度温度逐渐降低，保持机头温度为恒定温度(130～150℃范围内)。Step 1: Weigh each component within the mass fraction range as described above; Step 2: Surface treatment of the copper powder with a silane coupling agent; Step 3: Place the surface treated copper powder and polyethylene in the second step The high-speed high-shear mixing equipment is mixed and stirred, wherein the rotation speed of the equipment is set to 750 rpm, the temperature is set to 85 ° C, and the mixing time is set to 10 minutes; Step 4: uniformly mixing the high-speed high-shear mixing equipment in the third step The resulting material is fed into a twin-screw granulator to produce particles having the same particle size as the polyethylene plastic particles, i.e., as a biodegradable additive. The length-to-diameter ratio of the twin-screw granulator is 40, and the temperature control is very important. The temperature in the second zone is set to the highest temperature, that is, 180 °C, and the set temperature is maintained, so that the temperature of one zone is 5-15 °C lower than that of the second zone. Preferably, the temperature in the three zones and the four zones is substantially the same as that of the second zone, and the temperature of the three zones is gradually decreased from the five zones until the machine head is gradually lowered according to the gradient temperature, and the temperature of the head is kept constant (in the range of 130 to 150 ° C).
实施例1Example 1
表1：生物降解添加剂1的组成Table 1: Composition of biodegradable additive 1
组分Component 含量(质量％)Content (% by mass)
铜粉Copper powder 55
硅烷偶联剂A silane coupling agent 0.010.01
低密度聚乙烯Low-density polyethylene 94.9994.99
称取表1中所示质量比的铜粉、硅烷偶联剂及低密度聚乙烯；采用硅烷偶联剂对铜粉进行表面处理；将表面处理后的铜粉和低密度聚乙烯放入高速剪切混料设备内混合；将混合所得的混合料加入到双螺杆造粒机内，制成和聚乙烯塑料粒子形状相同，大小类似的颗粒。Weigh the copper powder, silane coupling agent and low density polyethylene in the mass ratio shown in Table 1; surface treatment of the copper powder with a silane coupling agent; and place the surface treated copper powder and low density polyethylene in the high speed The mixture is mixed in a shearing mixing device; the mixed mixture is added to a twin-screw granulator to prepare particles having the same shape and similar size as the polyethylene plastic particles.
实施例2Example 2
表2：生物降解添加剂2的组成Table 2: Composition of biodegradable additive 2
组分Component 含量(质量％)Content (% by mass)
铜粉Copper powder 55
硅烷偶联剂A silane coupling agent 0.050.05
低密度聚乙烯Low-density polyethylene 94.9594.95
除上表所示成分的不同外(如表2所示)，采用与实施例1相同的步骤制备生物降解添加剂2。The biodegradation additive 2 was prepared in the same manner as in Example 1 except for the difference in the ingredients shown in the above table (as shown in Table 2).
实施例3Example 3
表3：生物降解添加剂3的组成Table 3: Composition of biodegradable additive 3
组分Component 含量(质量％)Content (% by mass)
铜粉Copper powder 55
硅烷偶联剂A silane coupling agent 0.10.1
低密度聚乙烯Low-density polyethylene 94.994.9
除上表所示成分的不同外(如表3所示)，采用与实施例1相同的步骤制备生物降解添加剂3。The biodegradation additive 3 was prepared in the same manner as in Example 1 except for the difference in the ingredients shown in the above table (as shown in Table 3).
实施例4Example 4
表4：生物降解添加剂4的组成Table 4: Composition of biodegradable additive 4
组分Component 含量(质量％)Content (% by mass)
铜粉Copper powder 55
硅烷偶联剂A silane coupling agent 0.20.2
低密度聚乙烯Low-density polyethylene 94.894.8
除上表所示成分的不同外(如表4所示)，采用与实施例1相同的步骤制备生物降解添加剂4。The biodegradation additive 4 was prepared in the same manner as in Example 1 except for the difference in the ingredients shown in the above table (as shown in Table 4).
实施例5Example 5
表5：生物降解添加剂5的组成Table 5: Composition of biodegradable additive 5
组分Component 含量(质量％)Content (% by mass)
铜粉Copper powder 55
硅烷偶联剂A silane coupling agent 0.30.3
低密度聚乙烯Low-density polyethylene 94.794.7
除上表所示成分的不同外(如表5所示)，采用与实施例1相同的步骤制备生物降解添加剂5。The biodegradation additive 5 was prepared in the same manner as in Example 1 except for the difference in the ingredients shown in the above table (as shown in Table 5).
通过上述步骤制备的生物降解添加剂可直接按1～3质量％的比例添加到常规的塑料制品比如添加到聚乙烯塑料中而赋予其生物降解性能，加速其分解过程，使常规的塑料制品成为环境可降解塑料制品。该项技术特别适合用于生产环保型包装材料、一次性塑料制品、农用一次性薄膜(特别是地膜制品)等薄膜类塑料制品。这些制品在自然环境下，发生氧化反应，引起羧酸基团增加，使不能生物降解的塑料制品获得生物降解性能。这些环保类塑料制品最终降解为二氧化碳、水和腐殖质。以下结合实施例对其使用方法进行说明，但本发明并不限于此。The biodegradable additive prepared by the above steps can be directly added to a conventional plastic product in a proportion of 1-3 mass%, for example, added to a polyethylene plastic to impart biodegradability, accelerate the decomposition process, and make the conventional plastic product an environment. Degradable plastic products. This technology is particularly suitable for the production of environmentally friendly packaging materials, disposable plastic products, agricultural disposable film (especially film products) and other film plastic products. These products undergo an oxidation reaction in a natural environment, causing an increase in carboxylic acid groups to impart biodegradability to non-biodegradable plastic articles. These environmentally friendly plastic products eventually degrade into carbon dioxide, water and humus. The method of use thereof will be described below with reference to the embodiments, but the invention is not limited thereto.
可生物降解聚乙烯薄膜的制备和性能测试Preparation and performance testing of biodegradable polyethylene film
将上述生物降解添加剂1～5以2质量％、低密度聚乙烯(LDPE)88质量％、线性低密度聚乙烯(LLDPE)10质量％材料充分混合后，加入单螺杆挤出机(挤出机的长径比为20～30)，吹成厚度为25微米薄膜，将通过上述生物降解添加剂1～5制备的聚乙烯薄膜分别命名为聚乙烯薄膜A～E。The above biodegradable additives 1 to 5 are sufficiently mixed with 2% by mass, low density polyethylene (LDPE) 88% by mass, and linear low density polyethylene (LLDPE) 10% by mass, and then added to a single screw extruder (extruder). The aspect ratio of 20 to 30) was blown into a film having a thickness of 25 μm, and the polyethylene films prepared by the above biodegradable additives 1 to 5 were respectively named as polyethylene films A to E.
对制备的聚乙烯薄膜A～E分别进行紫外光照射(紫外光光源为发射340纳米波长光的紫外灯，强度为0.78±0.02W/m2·mm)和
Figure PCTCN2017108040-appb-000001
下热氧化处理，检测紫外光照射和加热前后的聚乙烯薄膜的纵向伸长率，结果如表6所示。The prepared polyethylene films A to E were respectively irradiated with ultraviolet light (the ultraviolet light source is an ultraviolet lamp emitting light of 340 nm wavelength, the intensity is 0.78±0.02 W/m 2 ·mm) and
Figure PCTCN2017108040-appb-000001
The thermal oxidation treatment was carried out to measure the longitudinal elongation of the polyethylene film before and after the ultraviolet light irradiation and heating, and the results are shown in Table 6.
表6：聚乙烯薄膜A～E降解前后的纵向伸长率变化Table 6: Longitudinal Elongation Changes of Polyethylene Films A to E before and after Degradation
Figure PCTCN2017108040-appb-000002
Figure PCTCN2017108040-appb-000002
Figure PCTCN2017108040-appb-000003
Figure PCTCN2017108040-appb-000003
由表6可知，掺入环保材料后，本发明的聚乙烯薄膜在光或热作用下，伸长率大大降低，即，聚乙烯薄膜发生了光和热降解。It can be seen from Table 6 that the elongation of the polyethylene film of the present invention under light or heat is greatly reduced after the incorporation of the environmentally friendly material, that is, the polyethylene film undergoes light and thermal degradation.
对参考薄膜(常规的聚乙烯薄膜，即组份为90％低密度聚乙烯，10％线性低密度聚乙烯)和添加本发明的生物降解添加剂制备而成的聚乙烯薄膜A～E进行纵向抗拉强度测试，结果如表7所示。Longitudinal resistance to the reference film (conventional polyethylene film, ie, component 90% low density polyethylene, 10% linear low density polyethylene) and polyethylene film A to E prepared by adding the biodegradable additive of the present invention Tensile strength test, the results are shown in Table 7.
表7：聚乙烯薄膜纵向抗拉强度(MPa)测试结果Table 7: Longitudinal tensile strength (MPa) test results of polyethylene film
Figure PCTCN2017108040-appb-000004
Figure PCTCN2017108040-appb-000004
由表7可知，本发明的聚乙烯薄膜相对于参考薄膜，抗拉强度得到了明显的改善，含有本发明的生物降解添加剂的聚乙烯薄膜的强度比不添加该生物降解添加剂的聚乙烯薄膜提高40％以上。As can be seen from Table 7, the tensile strength of the polyethylene film of the present invention is significantly improved relative to the reference film, and the strength of the polyethylene film containing the biodegradable additive of the present invention is higher than that of the polyethylene film without the biodegradation additive. 40% or more.
以上所述仅为本发明的较佳实施例，并非用来限定本发明的实施范围；如果不脱离本发明的精神和范围，对本发明进行修改或者等同替换，均应涵盖在本发明权利要求的保护范围当中。 The above is only the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. The invention is intended to be modified or equivalently substituted without departing from the spirit and scope of the invention. Within the scope of protection.

Claims (9)

  1. 一种含铜的生物降解添加剂，其特征在于，由以下组分组成：2～8质量％的铜粉、0.01％～0.30质量％的硅烷偶联剂、余量的低密度聚乙烯。A copper-containing biodegradation additive comprising: 2 to 8% by mass of copper powder, 0.01% to 0.30% by mass of a silane coupling agent, and the balance of low-density polyethylene.
  2. 根据权利要求1所述的含铜的生物降解添加剂，其特征在于，所述铜粉为粒径2微米以下的铜粉，用量为5质量％。The copper-containing biodegradation additive according to claim 1, wherein the copper powder is copper powder having a particle diameter of 2 μm or less, and the amount is 5% by mass.
  3. 根据权利要求1或2所述的含铜的生物降解添加剂，其特征在于，所述硅烷偶联剂为3-氨丙基三乙氧基硅烷。The copper-containing biodegradation additive according to claim 1 or 2, wherein the silane coupling agent is 3-aminopropyltriethoxysilane.
  4. 一种制备根据权利要求1～3的任一项所述的含铜的生物降解添加剂的方法，其特征在于，包含以下步骤：A method of preparing a copper-containing biodegradable additive according to any one of claims 1 to 3, comprising the steps of:
    步骤一：按比例称量各组分；Step 1: Weigh the components proportionally;
    步骤二：将铜粉用硅烷偶联剂进行表面处理；Step 2: surface treatment of copper powder with a silane coupling agent;
    步骤三：将经过所述步骤二的表面处理之后的铜粉和聚乙烯放入高速高剪切混料设备进行搅拌混合；Step 3: the copper powder and the polyethylene after the surface treatment of the second step are placed in a high-speed high-shear mixing device for stirring and mixing;
    步骤四：以双螺杆造粒机将通过步骤三均匀混合后的物料制成颗粒。Step 4: The material uniformly mixed by the third step is made into a pellet by a twin-screw granulator.
  5. 根据权利要求4所述的方法，在所述步骤三中，将所述高速高剪切混料设备的转速设为750rpm，温度设为85℃，混合时间设为10分钟。The method according to claim 4, wherein in the third step, the rotation speed of the high-speed high-shear mixing device is set to 750 rpm, the temperature is set to 85 ° C, and the mixing time is set to 10 minutes.
  6. 根据权利要求4所述的方法，其特征在于，在所述步骤四中，所述双螺杆造粒机的长径比为40。The method according to claim 4, wherein in said step four, said twin-screw granulator has an aspect ratio of 40.
  7. 根据权利要求4所述的方法，其特征在于，在所述步骤四中，设定二区温度为最高温度，即180℃，保持该设定的温度，使一区比二区温度低10℃，使三区、四区温度与二区相同，从五区开始直至机头按梯度逐渐降低，保持机头温度为恒定温度。The method according to claim 4, wherein in the step four, the temperature of the two zones is set to a maximum temperature, that is, 180 ° C, and the set temperature is maintained, so that a zone is 10 ° C lower than the temperature of the second zone. The temperature in the three zones and four zones is the same as that in the second zone. From the five zones until the nose gradually decreases according to the gradient, the temperature of the head is kept constant.
  8. 一种塑料制品，其特征在于，含有根据权利要求1～3的任一项所述的含铜的生物降解添加剂1～3质量％。A plastic product comprising 1 to 3 mass% of the copper-containing biodegradation additive according to any one of claims 1 to 3.
  9. 一种聚乙烯薄膜制品，其特征在于，含有根据权利要求1～3的任一项所述的含铜的生物降解添加剂1～3质量％。 A polyethylene film product comprising the copper-containing biodegradation additive according to any one of claims 1 to 3 in an amount of 1 to 3% by mass.
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