CN1396199A - Degradable mother particles of plastics for protecting environment - Google Patents
Degradable mother particles of plastics for protecting environment Download PDFInfo
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- CN1396199A CN1396199A CN 02138841 CN02138841A CN1396199A CN 1396199 A CN1396199 A CN 1396199A CN 02138841 CN02138841 CN 02138841 CN 02138841 A CN02138841 A CN 02138841A CN 1396199 A CN1396199 A CN 1396199A
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Abstract
A degradable mother material of plastics is prepared from white sludge generated by making paper or refining sugar, polyslefin, optical trigger, bioactivity decreaser, assistant, and coupling agent. Its advantages are low cost and no environmental pollution.
Description
Technical Field
The invention relates to a degradable plastic master batch, in particular to a master batch for preparing degradable plastic.
Background
Plastics are the most widely used materials after wood, steel and cement, and have already existed in the first place of the world in terms of volume, and the world plastic yield is about 1.5 hundred million tons in 1998. But the huge 'white pollution' which is difficult to degrade seriously pollutes the environment. In addition, the raw materials for producing plastics are non-renewable petroleum resources, and the petroleum storage capacity is becoming smaller and smaller, and the worldwide petroleum production is reported to be only forty years old. Therefore, it is urgent to find new materials that are environmentally friendly and can replace petroleum resources. The implementation of resource saving (reduction), resource recycling (recycling) and active development of environmentally degradable plastics are important conditions and effective means while improving the environmental awareness of people. The degradable plastics can be divided into light degradable plastics, biological degradable plastics and light-biological double degradable plastics according to the degradation mechanism.
Photodegradable Plastics (photogradeable Plastics): the energy for light degradation is mainly from ultraviolet rays in sunlight, and certain polymers can undergo an automatic oxidation reaction under the action of oxygen in air. However, the photodegradation characteristics of polymers in general are not significant because the photodegradation characteristics are related to the structure of the polymer. The method for solving the problem of plastic degradation comprises two methods: (1) the photodegradable plastic resin is obtained by introducing photosensitive groups on the polymer and carrying out copolymerization reaction with the polymer. (2) In the plastic processing process, the photodegradable plastic is obtained by adding a small amount of photosensitizer. These photosensitizers usually carry chromophoric groups, which lead to the generation of active free radicals by the initiating action of the photosensitizers, thereby accelerating the photodegradation process of the polymers. Besides organic compounds, the photosensitizer also contains inorganic compounds such as manganese, iron, cobalt, nickel, copper, chromiumand the like, and the service life of the polymer product and the time required for finishing the photodegradation reaction can be regulated and controlled by adjusting the addition amount of the photosensitizer. However, the photodegradable plastic has higher dependence on the irradiation intensity and the irradiation time, and the controllability of the degradation time is poorer, so that the buried part and the waste entering a garbage system cannot be degraded.
Biodegradable plastics (biodegradable Polymers) are mostly prepared by adding additives into biodegradable materials such as starch or modified starch, Polycaprolactone (PCL) and the like. Although the biodegradable plastics can be completely degraded, the natural polymer materials have many defects compared with synthetic resin, most of the natural polymer materials do not have heating and fusible thermoplasticity, are difficult to form by a conventional plastic processing method, have large processing difficulty, complex process and poor physical and mechanical properties, have great difference in strength in dry and wet environments, cannot be recycled and have high cost.
The invention patent of CN1273252 discloses an inorganic base material composite degradable plastic master batch, the combination of the plastic master batch comprises an inorganic composite base material, composite polyolefin, a lubricating additive and a coupling additive. TheThe plastic master batch has the advantages of simple production process, low processing cost and excellent physical and chemical properties of products, and the prepared plastic products are thoroughly degraded and have controllable degradation induction period. However, the inorganic base material composite degradable plastic has the following defects; (1) biodegradation of reaction products mainly by the Nordic reaction IWherein the hydroxyl group is attacked by the microorganisms according to the following reaction formula
The quantum yield of the reaction I and the reaction II is determined, and the result shows that both products can be obtained, but the quantum yield of the reaction I at normal temperature is only 1/100 of the reaction II, so the possibility of biodegradation is small. (2) No bioactive degradation promoter, and no ability to accelerate the degradation of residual membrane.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide the degradable plastic master batch which has the advantages of easily obtained raw materials, simple production process, low processing cost, quick and thorough degradation and no pollution to the environment.
The environment-friendly degradable plastic master batch provided by the invention is prepared by taking white mud or cane sugar white mud of a straw pulp and paper mill as a base material, taking polyolefin as a petroleum byproduct as a carrier resin, adding a photosensitization initiator, a biological activity degradation promoter, a coupling agent and a processing aid, and extruding and granulating by a high-length-diameter ratio high-shear double-screw extruder, wherein the components are prepared by the following weight ratio: 60-85 parts of papermaking white mud or sucrose white mud, 10-30 parts of polyolefin, 1-3 parts of a photo-sensitizing initiator, 0.1-0.3 part of a biological activity degradation promoter, 0.5-2.5 parts of a processing aid and 0.5-2.5 parts of a coupling agent.
When the white mud in the components is waste residue discharged by a straw pulp paper mill, the main component is calcium carbonate (about 85-90%), the white mud can be used after being dried and screened, harmful heavy metalsare not contained, the white mud is an environment-friendly material, the whiteness is required to be more than 85%, and the white mud contains a small amount of lignin, cellulose and hemicellulose and can be corroded by microorganisms.
Polyolefins including Polyethylene (PE), polypropylene (PP), Polystyrene (PS) are used as the carrier resin. One or more of the polyolefins of different types can be used according to the proportion.
The light sensitization initiator is active metal ions or carbonyl compounds. Such as metal salts of stearic acid or anatase titanium dioxide or calcium carbonate or substances having the following photosensitizing groups: -CH-CH-, -CH2-、-C≡C-、-N＝N-、-NH-、-NH-NH-、-S-。
The bioactive degradation promoter is chemical substance containing element (N), phosphorus (P) and potassium (K), such as urea, potassium chloride, calcium phosphate or slow release fertilizer based on EVA (ethylene/vinyl acetate copolymer) and LDPE (low density polyethylene).
The processing aid is one or more of stearic acid and salts thereof. For example, calcium stearate is used as an internal lubricant and stearic acid is used as an external lubricant in a synergistic manner, and has a heat stabilizing effect.
The coupling agent is an aluminum-titanium composite coupling agent or a rare coupling agent.
In order to increase the compatibility of two completely different components of white mud and polyolefin, the white mud is activated by adopting an aluminum-titanium composite coupling agent firstly, the method comprises the steps of stirring and heat drying the white mud in a high-speed mixer for 10 minutes (the temperature is 90-110 ℃), then adding metered coupling agent for three times, and adding the coupling agent to discharge every 2 minutes, wherein the total time is 10 minutes.
Pure polyolefins generally absorb uv light at a low rate and are also difficult to degrade by uv light, such as Polyethylene (PE) which has a low photodegradation quantum efficiency.
Photodegradation quantum efficiency of PE
| Wavelength nm | Quantum efficiency of carbonyl generationRate of change |
| 254 | 0.04 |
| 2.50-350 | 0.11 |
| 3.50-45.0 | 0.00 |
Note: quantum efficiency refers to the number of molecules that ultimately form a decomposition per amount absorbed. The larger the value, the faster the degradation rate.
When a photosensitizing initiator such as transition metal ion, carbonyl compound, etc. is introduced into polyolefin, and in the presence of oxygen, such as metal salt of stearic acid, anatase titanium dioxide, calcium carbonate or a substance having a photosensitizing group as follows: -CH-CH-, -CH2-、-C≡C-、
-N ═ N-, -NH-, -S-, and in the presence of oxygen, they can absorb the transition of a photon (h γ) in ultraviolet light from the ground state (S) to the excited state (S)*)
Excited (S)*) Will transfer energy to the polymer (RH) of the polyolefin, causing it to generate a polymer radical R (primary radical)
The free radical cannot produce photolysis, and can react with oxygen in the air to generate a polymer peroxide free radical ROO
ROO-Generation of a Secondary free radical R. by chain reaction
The secondary free radical (R.cndot.) is photolyzed, and the length of the degradation induction period depends on the time required for the generated secondary free radical to reach the photolytic concentration. Therefore, by selecting different types of photo-sensitization initiators or changing the addition amount of the photo-sensitization initiators, the length of the degradation induction period can be regulated and controlled, and the controllability of the photo-degradation is realized.
The lignin, cellulose and hemicellulose in the white mud are natural biodegradable materials. Containing carboxyl groups, i.e. CH, at the ends of the low molecular weight products obtained by photooxidation2-CH2The (COOH) in COOH can be eroded by microbe to produce biodegradation function, and the biological activity degradation promoter added in the invention, such as urea, potassium chloride, calcium phosphate or slow-release fertilizer using EVA (ethylene/vinyl acetate copolymer) and LDPE (low-density polyethylene) as base material can promote the activity of microbe and is helpful for biodegradation, so that the degradable plastic has obvious biodegradation characteristic, and can ensure that the degradable plastic has good biodegradation property when used as garbage landfill.
The master batches for the degradable plastics according to the invention are used with processing aids, such as stearates of certain metals, for example calcium (C) stearate17H35COOaOCC17H35) The molecule of (A) is connected by two long carbon chains through a polar groupAnd (4) connecting. Due to hard fatThe acid salt has strong affinity to calcium ions, can cover the surface of calcium carbonate which is the main component in the white mud, and prevents the occurrence of a light sensitization initiating process, thereby ensuring that the performance of the degradable plastic is not changed and the degradable plastic is not degraded in a general storage period.
Compared with the prior art, the degradable plastic master batch provided by the invention has the following advantages: 1. the raw materials are factory waste materials and are easy to obtain. 2. The production process is simple and the processing cost is low. 3. The main raw material white mud contains lignin, cellulose and hemicellulose, is a natural biodegradable material, has a biodegradation function, and is reasonable in component formula, so that the product is degraded quickly and completely, and after degradation, the added bioactive degradation substances can improve the soil fertility. 4. No pollution to environment.
Detailed Description
Example 1:
the preparation method comprises the following steps:
LDPE (1F7B) 10 parts
85 portions of white mud
Al-Ti composite coupling agent OL-AT 16181 parts
HSt 2 parts
1 part of CaSt
Brightener XH-202B 1 parts
0.1 portion of urea
Example 2:
the preparation method comprises the following steps:
random PP 15 parts
85 portions of white mud
Al-Ti composite coupling agent OL-AT 16181.5 parts
HSt 1 portion
1 part of CaSt
Brightener XH-202B 1 parts
Potassium chloride calcium phosphate 0.1 part
Example 3:
the preparation method comprises the following steps:
HDPE (MI: 10-15) 25 parts
70 portions of white mud
Rare earth coupling agent XL-9551 parts
HSt 2 parts
FeSt 1 part
Brightener XH-202B 1 parts
0.1 part of slow-release compound fertilizer
Claims (8)
1. The environment-friendly degradable plastic master batch is characterized by being prepared by mixing the following components in parts by weight: 60-85 parts of papermaking white mud or sucrose white mud, 10-30 parts of polyolefin, 1-3 parts of a photo-sensitizing initiator, 0.1-0.3 part of a biological activity degradation promoter, 0.5-2.5 parts of a processing aid and 0.5-2.5 parts of a coupling agent.
2. The degradable plastic masterbatch of claim 1, wherein said lime mud contains 85% to 90% calcium carbonate component, has a whiteness of greater than 85%, and contains a small amount of lignin, cellulose and hemicellulose.
3. The master batch of degradable plastics according to claim 1, wherein said polyolefin is one or more of polyethylene, polypropylene and polystyrene.
4. A degradable plastic masterbatch according to claim 1 wherein said photo-sensitizing initiator is a reactive metal ion or a carbonyl compound.
5. A master batch for degradable plastics according to claim 1 or 4, wherein said photo-sensitizing initiator is a metal salt of stearic acid or anatase titanium dioxide or calcium carbonate or a substance having a photo-sensitizing group as follows: -CH-CH-, -CH2-、-C≡C-、
-N＝N-、-NH-、-NH-NH-、-S-。
6. A degradable plastics masterbatch according to claim 1, wherein said bioactive degradation promoteris a chemical substance containing nitrogen, phosphorus and potassium, such as one or more of urea, potassium chloride, calcium phosphate, slow release fertilizers based on ethylene/vinyl acetate copolymer, low density polyethylene.
7. A masterbatch of degradable plastics according to claim 1 wherein said processing agent is stearic acid or one or more of its salts.
8. The master batch for degradable plastics according to claim 1, wherein said coupling agent is an aluminum-titanium composite coupling agent or a rare earth coupling agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02138841 CN1396199A (en) | 2002-07-26 | 2002-07-26 | Degradable mother particles of plastics for protecting environment |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02138841 CN1396199A (en) | 2002-07-26 | 2002-07-26 | Degradable mother particles of plastics for protecting environment |
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| CN1396199A true CN1396199A (en) | 2003-02-12 |
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| CN 02138841 Pending CN1396199A (en) | 2002-07-26 | 2002-07-26 | Degradable mother particles of plastics for protecting environment |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL2009601C2 (en) * | 2012-10-09 | 2014-04-14 | Barracuda Products B V | Biological polymeric matrix component. |
| CN103896992A (en) * | 2014-04-17 | 2014-07-02 | 齐鲁工业大学 | Method for preparing oligosaccharides from lignocellulosic hydrolyzate |
| CN104829873A (en) * | 2015-04-10 | 2015-08-12 | 合肥环照高分子材料厂 | Kelp powder biodegradable plastic and preparation method thereof |
| CN105504725A (en) * | 2016-01-29 | 2016-04-20 | 常州市鼎升环保科技有限公司 | Method for preparing polylactic acid composite material by modifying papermaking white mud |
| CN105985657A (en) * | 2015-02-06 | 2016-10-05 | 天津毅兴彩科技有限公司 | Antimicrobial degradable plastic masterbatch |
| CN107513229A (en) * | 2017-09-01 | 2017-12-26 | 重庆卡美伦科技有限公司合川分公司 | A kind of environmentally friendly polrvinyl benzene composite board material and preparation method thereof |
| CN107987544A (en) * | 2017-11-06 | 2018-05-04 | 湖南望隆企业管理咨询有限公司 | A kind of low cost degradation plastic and preparation method thereof |
-
2002
- 2002-07-26 CN CN 02138841 patent/CN1396199A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL2009601C2 (en) * | 2012-10-09 | 2014-04-14 | Barracuda Products B V | Biological polymeric matrix component. |
| WO2014084724A1 (en) * | 2012-10-09 | 2014-06-05 | Hemcell B.V. | Melt processed polymer composition derived from leaf sheaths of trees of the genus arecaceae |
| US9914834B2 (en) | 2012-10-09 | 2018-03-13 | Hemcell B.V. | Melt processed polymer composition derived from leaf sheaths of trees of the genus Arecaceae |
| US10526490B2 (en) | 2012-10-09 | 2020-01-07 | Hemcell B.V. | Melt processed polymer composition derived from leaf sheaths of trees of the genus Arecaceae |
| CN103896992A (en) * | 2014-04-17 | 2014-07-02 | 齐鲁工业大学 | Method for preparing oligosaccharides from lignocellulosic hydrolyzate |
| CN103896992B (en) * | 2014-04-17 | 2016-05-25 | 齐鲁工业大学 | A kind of method of producing compound sugar from ligno-cellulose hydrolysate |
| CN105985657A (en) * | 2015-02-06 | 2016-10-05 | 天津毅兴彩科技有限公司 | Antimicrobial degradable plastic masterbatch |
| CN104829873A (en) * | 2015-04-10 | 2015-08-12 | 合肥环照高分子材料厂 | Kelp powder biodegradable plastic and preparation method thereof |
| CN105504725A (en) * | 2016-01-29 | 2016-04-20 | 常州市鼎升环保科技有限公司 | Method for preparing polylactic acid composite material by modifying papermaking white mud |
| CN107513229A (en) * | 2017-09-01 | 2017-12-26 | 重庆卡美伦科技有限公司合川分公司 | A kind of environmentally friendly polrvinyl benzene composite board material and preparation method thereof |
| CN107987544A (en) * | 2017-11-06 | 2018-05-04 | 湖南望隆企业管理咨询有限公司 | A kind of low cost degradation plastic and preparation method thereof |
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