CN107177339A - A kind of biodegradable lactide oligomer adhesive and its production and use - Google Patents
A kind of biodegradable lactide oligomer adhesive and its production and use Download PDFInfo
- Publication number
- CN107177339A CN107177339A CN201710440686.XA CN201710440686A CN107177339A CN 107177339 A CN107177339 A CN 107177339A CN 201710440686 A CN201710440686 A CN 201710440686A CN 107177339 A CN107177339 A CN 107177339A
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- Prior art keywords
- chemosynthesis
- adhesive
- reaction
- solvent
- adhesion agent
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
- C09J167/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/85—Germanium, tin, lead, arsenic, antimony, bismuth, titanium, zirconium, hafnium, vanadium, niobium, tantalum, or compounds thereof
Abstract
The present invention relates to a kind of biodegradable adhesive material prepared using lactide (LA) chemosynthesis product; by 5% 50% ratios of the LA materials in solvent quality; pour into the reaction vessel equipped with solvent; reactor band is stirred and temperature controlling function; control reactor under nitrogen protection; control certain reaction temperature; it is stirred simultaneously; after LA meltings completely; catalyst is added, after reaction a period of time, stops stirring; extraction centrifugation is carried out after taking-up, that is, obtains LA chemosynthesis products.Then, lactide (LA) chemosynthesis product is dissolved with ethyl acetate, obtains biological degradation adhesion agent.The adhesive has the characteristics of preparing simple, relative molecular weight and controllable and biodegradable viscosity, is fixed available for adhesive tape, leather, paster, stationery, office, electronics, automobile edging, footwear industry, manual ornaments paste the field such as fixed.
Description
Technical field
This technology is related to chemical material field, particularly a kind of to be prepared using lactide (LA) chemosynthesis product
Biodegradable adhesive material and preparation method thereof.
Background technology
At present, the type of in the market adhesive is relatively more, is all played in the various industries such as adhesive tape, stationery, manual ornaments
Extremely important effect.Although most products in tack, hold viscosity, meet the requirements in terms of peel strength, in ring
But there is larger hidden danger in terms of ensuring safety.Due to traditional adhesive in natural environment be difficult degraded, be applied to plastics,
After the products such as leather, paper, enter environment after being gone out of use with these products, " pollution " caused due to that can not degrade, into
For the major hidden danger of conservation of natural environment, the problem in this respect that solves is increasingly becoming the focus currently researched and developed.
In recent years, a few studies personnel begin one's study degradable adhesive, for example, CN00128743.5 is reported by poly- day
The Water-soluble adhesive that the mixture of winter propylhomoserin, its salt and its derivative and natural thickener resin is made.Although in the patent
It is described as biodegradable, but specifically demonstrates the biological degradation rate of mixture adhesive is how many on earth.In addition, water
The poor-performings such as water resistance, solvent resistance, the glued membrane intensity of property adhesive, and analyzed according to synthesis technique, its cost is also very high.
Generally speaking, the development for producing low, the biodegradable adhesive of simple, easy to operate, cost is still rarely found.
The content of the invention
It is an object of the invention to provide it is a kind of using lactide (LA) chemosynthesis product prepare it is biodegradable
Adhesive material, the adhesive has the characteristics of preparing simple, relative molecular weight and controllable viscosity, available for adhesive tape, leather,
Paster, stationery, office, electronics, automobile edging are fixed, footwear industry, manual ornaments paste the field such as fixed.
Biological degradation adhesion agent of the present invention, its raw material is based on constituent mass fraction, including following components：
10-90 parts of lactide (LA) chemosynthesis product；
10-90 parts of solvent.
Biological degradation adhesion agent of the present invention, viscosity is 50-5000mPaS, peel strength >=2.5 (N/cm), just
Viscous force (ball number) >=5, holding power >=0.8h, Relative biological resolution ratio >=90%.
The preparation method of lactide (LA) chemosynthesis product in biological degradation adhesion agent of the present invention, including with
Lower step：5%-50% ratio of the LA materials in solvent quality is poured into the reaction vessel equipped with solvent, the stirring of reactor band
With temperature controlling function, control reactor under nitrogen protection, controls certain reaction temperature, is stirred simultaneously, after LA meltings completely,
Catalyst is added, after reaction a period of time, stops stirring, carries out purification centrifugation, that is, obtain LA chemosynthesis products.
Catalyst according to claim 1-3 is stannous octoate, and described solvent is ethyl acetate.
Temperature of reactor during chemosynthesis reaction according to claim 3 can be in 30 DEG C~75 DEG C intervals
Any temperature, the chemosynthesis reaction time can be 3h~12h.
Biological degradation adhesion agent preparation method according to claim 1-5, it is characterised in that produce LA chemical syntheses
Thing is diluted appropriate viscosity with ethyl acetate, that is, obtains biological degradation adhesion agent.
Above-mentioned biological degradation adhesion agent, consolidates available for adhesive tape, leather, paster, stationery, office, electronics, automobile edging
Fixed, footwear industry, manual ornaments are pasted in terms of fixing.
Compared with prior art, beneficial effects of the present invention are：
(1) the preparation initial feed of adhesive is biodegradable biological manufacture lactide (LA) so that final product
The biological degradability of adhesive can ensure；
(2) because the method for taking synthesis LA carries out scheme processing, it is possible to by controlling the usage amount of catalyst, changing
The relative molecular weight that synthesis reaction temperature, reaction time control synthetic product is learned, so that the viscosity to control product so that most
Whole adhesive viscosity is controllable；
(3) due to being to take ethyl acetate dissolved dilution LA chemosynthesis products, ethyl acetate small toxicity and water is dissolved in, institute
With more environment-friendly and safer relative to traditional benzene series solvent-based adhesive；
(4) adhesive product processing technology it is simple, without adding other auxiliary agents, continuous production, efficiency high can be carried out；
(5) at present because in the biological degradation adhesion agent of invention, the concentration of lactide (LA) chemosynthesis product is very
In the case of low, you can meet the viscosity needed for adhesive, therefore so that adhesive cost is relatively low.
Due to possessing above-mentioned advantage so that biological degradation adhesion agent can be used for adhesive tape, paster, stationery, office, electronics,
Automobile edging is fixed, footwear industry, manual ornaments paste the field such as fixed, not only with environment protection significance, and is had a wide range of applications
Prospect.
Embodiment
The embodiment to the present invention is described in further detail below.Following examples are used to illustrate the present invention,
But it is not limited to the scope of the present invention.
Embodiment 1~4
(1) in embodiment prepared by LA chemosynthesis products
Ethyl acetate solution is separately added into four reactors, then in 25% ratio of ethyl acetate solution quality
LA powders are added, under nitrogen protection, control temperature is at 60 DEG C, and mixing speed is 150r/min, after LA is completely dissolved, and adds
2.12g stannous octoates, take out reactant when reacting respectively after 2.5h, 4h, 6h, 9h, carry out purification centrifugation with absolute ethyl alcohol, obtain
LA chemosynthesis products.
(2) LA chemosynthesis products performance characterization in embodiment
1. nuclear magnetic resonance is tested
Nuclear magnetic resonance experiment condition is that solvent is heavy water, internal standard tetramethylsilane.There is PLA methine base in nuclear-magnetism figure
The quadruple peak center of group is 1.5ppm in 5.2ppm, methyl displacement peak value, illustrates there is the production of LA macromoleculars in the copolymer after cleaning
Thing.
2. gpc analysis
GPC experiment conditions are, tetrahydrofuran mobile phase, sample concentration 2-3mg/ml, flow velocity 1ml/min, detection temperature 30
DEG C, standard sample polystyrene (PS).Differential responses time gpc analysis LA chemosynthesis product number-average molecular weight the results are shown in Table 1.
Table 1
Example 5~8
Example 4 is obtained into LA chemosynthesis products to be diluted with ethyl acetate, obtained biological degradation adhesion agent.Foundation
The solid content of solution, takes volumetric soiutions uniformly to be applied with scraper and scrapes on brown paper, be put into baking oven and dry 10min, and gel content is made
For 12mg/cm2Pressure sensitive adhesive tape.Rolling ball method (angle of inclination in inclined-plane in national standard GB/T4852-2002 is taken in wherein initial bonding strength test
30 °, sample long more than 250mm, wide 10-80mm), detect the maximum ball size that the adhesive faces of specific length can be clung.Hold
Viscous force test take adhesive tape in national standard GB/T4851-2014 to the method for testing of standard testing steel plate (sample long 150mm, it is wide
12 ± 0.5mm), adhesive tape is measured by the out-of-service time of adhesive tape viscosity is held to standard steel plate；According to national standard GB/T
180 ° of disbonded tests of adhesive tape and stainless steel plate measure peel strength in 2792-2014.Measured according to national standard GB/T2754-95
Viscosity.The properties of biological degradation adhesion agent are shown in Table 2.
Table 2
Biological degradation adhesion agent is obtained with example 8, using biaxially stretched polylactic acid film as base material, express mail service encapsulation is prepared
With adhesive tape, the performance for preparing adhesive tape is as shown in table 3.
Table 3
Note：Measured according to postal industry encapsulation with adhesive tape (biodegradable band) standard.Wherein initial bonding strength national standard GB/T4852-
Inclined-plane rolling ball method (method is ibid) and skewed slot rolling ball method (21 ° 30 ' of inclination angle long more than 100mm, wide 25mm) measure it in 2002
The distance rolled on adhesive tape adhesiveness face on level board.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, without departing from the technical principles of the invention, some improvement and modification can also be made, these improvement and modification
Also it should be regarded as protection scope of the present invention.
Claims (7)
1. a kind of biodegradable adhesive and preparation method thereof, it is characterised in that the composition of the adhesive is：
10-90 parts of lactide (LA) chemosynthesis product；
10-90 parts of solvent.
2. biological degradation adhesion agent according to claim 1, is characterised by, viscosity is 50-5000mPaS, peel strength
>=2.5 (N/cm), initial bonding strength (ball number) >=5, holding power >=0.8h, Relative biological resolution ratio >=90%.
3. lactide (LA) chemosynthesis product according to claim 1,2, its preparation method is to comprise the following steps：
5%-50% ratio of the LA materials in solvent quality is poured into the reaction vessel equipped with solvent, the stirring of reactor band and temperature control
Function, control reactor under nitrogen protection, controls certain reaction temperature, is stirred simultaneously, and after LA meltings completely, addition is urged
Agent, after reaction a period of time, stops stirring, carries out purification centrifugation, that is, obtain LA chemosynthesis products.
4. the catalyst according to claim 1-3 is stannous octoate, described solvent is ethyl acetate.
5. temperature of reactor during chemosynthesis reaction according to claim 3 can be appointing in 30 DEG C~75 DEG C intervals
One temperature, the chemosynthesis reaction time can be 3h~12h.
6. the biological degradation adhesion agent preparation method according to claim 1-5, it is characterised in that by LA chemosynthesis products
Appropriate viscosity is diluted with ethyl acetate, that is, obtains biological degradation adhesion agent.
7. the biological degradation adhesion agent prepared according to claim 1~6, available for adhesive tape, leather, paster, stationery, office, electricity
Son, automobile edging are fixed, footwear industry, manual ornaments are pasted in terms of fixing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710440686.XA CN107177339B (en) | 2017-06-12 | 2017-06-12 | Biodegradable lactide oligomer adhesive and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710440686.XA CN107177339B (en) | 2017-06-12 | 2017-06-12 | Biodegradable lactide oligomer adhesive and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107177339A true CN107177339A (en) | 2017-09-19 |
| CN107177339B CN107177339B (en) | 2020-08-11 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201710440686.XA Active CN107177339B (en) | 2017-06-12 | 2017-06-12 | Biodegradable lactide oligomer adhesive and preparation method and application thereof |
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| Country | Link |
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| CN (1) | CN107177339B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108250368A (en) * | 2018-01-18 | 2018-07-06 | 中国科学院长春应用化学研究所 | A kind of biodegradable pressure-sensitive adhesive agent and preparation method thereof |
| EP4230659A1 (en) | 2022-02-22 | 2023-08-23 | Organik Kimya San. Ve Tic. A.S. | Biodegradable bimodal polymers and method for producing them. |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5312850A (en) * | 1993-01-04 | 1994-05-17 | National Starch And Chemical Investment Holding Corporation | Polylactide and starch containing hot melt adhesive |
| EP0899274A1 (en) * | 1997-08-26 | 1999-03-03 | National Starch and Chemical Investment Holding Corporation | Lactide graft copolymers and hot melt adhesives prepared from same |
| CN1556142A (en) * | 2004-01-09 | 2004-12-22 | 中国科学院长春应用化学研究所 | Preparation method of biodegradable polyester composite material |
| CN103739833A (en) * | 2014-01-15 | 2014-04-23 | 苏州大学 | Method for preparing polylactide |
| US20160304751A1 (en) * | 2013-11-18 | 2016-10-20 | Tesa Se | Adhesive tape for covering elongated goods, such as cable sets in particular, and method for covering |
-
2017
- 2017-06-12 CN CN201710440686.XA patent/CN107177339B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5312850A (en) * | 1993-01-04 | 1994-05-17 | National Starch And Chemical Investment Holding Corporation | Polylactide and starch containing hot melt adhesive |
| EP0899274A1 (en) * | 1997-08-26 | 1999-03-03 | National Starch and Chemical Investment Holding Corporation | Lactide graft copolymers and hot melt adhesives prepared from same |
| CN1556142A (en) * | 2004-01-09 | 2004-12-22 | 中国科学院长春应用化学研究所 | Preparation method of biodegradable polyester composite material |
| US20160304751A1 (en) * | 2013-11-18 | 2016-10-20 | Tesa Se | Adhesive tape for covering elongated goods, such as cable sets in particular, and method for covering |
| CN103739833A (en) * | 2014-01-15 | 2014-04-23 | 苏州大学 | Method for preparing polylactide |
Non-Patent Citations (1)
| Title |
|---|
| 段久芳: "《天然高分子材料》", 30 September 2016, 华中科技大学出版社 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108250368A (en) * | 2018-01-18 | 2018-07-06 | 中国科学院长春应用化学研究所 | A kind of biodegradable pressure-sensitive adhesive agent and preparation method thereof |
| CN108250368B (en) * | 2018-01-18 | 2021-02-05 | 中国科学院长春应用化学研究所 | Biodegradable pressure-sensitive adhesive and preparation method thereof |
| EP4230659A1 (en) | 2022-02-22 | 2023-08-23 | Organik Kimya San. Ve Tic. A.S. | Biodegradable bimodal polymers and method for producing them. |
| WO2023161081A1 (en) | 2022-02-22 | 2023-08-31 | Organik Kimya Sanayi Ve Tic. A.S. | Waterborne biodegradable polymer composition |
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| CN107177339B (en) | 2020-08-11 |
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