CN110938188A - Biodegradable polyurethane composite material for packaging and preparation method thereof - Google Patents
Biodegradable polyurethane composite material for packaging and preparation method thereof Download PDFInfo
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- C08G18/6611—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
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Abstract
The invention belongs to the technical field of polyurethane, and particularly relates to a biodegradable polyurethane composite material for packaging and a preparation method thereof. The mass ratio of 1: 1.0-1.5 of a component A and a component B, wherein: the component A is prepared from the following raw materials: polycaprolactone A, polycaprolactone B, polylactic acid, a cross-linking agent, a chain extender, a foam stabilizer, a surfactant, water, a composite catalyst and an auxiliary agent; the component B is prepared from the following raw materials: polyether polyol, small molecular alcohol and diphenylmethane diisocyanate. The polyurethane foam prepared by the polyurethane composite material for biodegradable packaging has biodegradability, the packaging material can be biodegraded after being buried for 3-5 years after being used, and the decomposed organic matter is small in fragment and further decomposed into carbon dioxide and water, so that the environment-friendly effect is achieved.
Description
Technical Field
The invention belongs to the technical field of polyurethane, and particularly relates to a biodegradable polyurethane composite material for packaging and a preparation method thereof.
Background
Polyurethane foam is prepared by reacting isocyanate and polyol compounds for foaming, and is mainly divided into hard and soft polyurethane foams. Polyurethane foams have excellent physical and mechanical properties, acoustic properties, electrical properties and chemical resistance. The density and hardness of the polyurethane foam plastic can be changed by adjusting the raw materials and the formula. In addition, the polyurethane foam plastic is convenient and simple to construct and mold, and can be cured and molded into products with required shapes according to the size and the type of the mold.
The polyurethane foam can be applied to the packaging industry, and especially plays an important role in the field of seamless filling of equipment and instruments. However, the traditional polyurethane packaging material is a product formed by crosslinking and curing polyether polyol and isocyanate, and after the traditional polyurethane packaging material is used as thermosetting plastic, the traditional polyurethane packaging material is difficult to degrade in natural environment and causes serious pollution to the environment.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: overcomes the defects of the prior art, and provides a biodegradable polyurethane composite material for packaging; the polyurethane foam prepared by the composite material has biodegradability while ensuring excellent foam strength and mechanical properties; the invention also provides a preparation method thereof.
The invention relates to a biodegradable polyurethane composite material for packaging, which is prepared from the following components in percentage by mass of 1: 1.0-1.5 of a component A and a component B, wherein:
the component A is prepared from the following raw materials in parts by mass:
the component B is prepared from the following raw materials in parts by mass:
10-20 parts of polyether polyol
2-5 parts of small molecular alcohol
60-85 parts of diphenylmethane diisocyanate.
Wherein:
the hydroxyl value of polycaprolactone A is 320-560mgKOH/g, the functionality is 3, the viscosity at 30 ℃ is 400-850 mpa.s, and the water content is less than 0.05 wt%; preferably the model PCL303 with the functionality of 3, the hydroxyl value of 380-440mgKOH/g and the viscosity of 600-800 mpa.s at 30 ℃.
The hydroxyl value of polycaprolactone B is 200-; preferably PCL205 with a functionality of 2, a hydroxyl value of 200 and 240mgKOH/g, and a viscosity of 250 to 350mpa.s at 30 ℃.
The polylactic acid (PLA) has a hydroxyl value of 200-300mgKOH/g, a functionality of 2, a viscosity of 5000-8000 mpa.s at 25 ℃, and a water content of less than 0.05 wt%.
The crosslinker is a trifunctional, small molecule alcohol, preferably Triethanolamine (TEA), and less preferably glycerol.
The chain extender is difunctional micromolecular alcohol, preferably one or more of Ethylene Glycol (EG), 1, 4-butanediol (1, 4-BG), dipropylene glycol or diethylene glycol.
The foam stabilizer is a polysiloxane-oxyalkylene block copolymer, preferably of the type DC6070 available from Air Products, USA, and more preferably DC2525 available from Air Products, USA.
The surfactant is a silicone surfactant, preferably foam stabilizer L-580 produced by Meiji organosilicon materials (Shanghai) Co., Ltd.
The composite catalyst is a mixture of N, N '-dimethylcyclohexylamine, N' -dimethylbenzylamine and bis (dimethylaminoethyl) ether.
The auxiliary agent is a diluent, and the diluent is propylene carbonate.
The polyether polyol in the component B is INOVORL 330N.
The small molecular alcohol in the component B is 1, 4-butanediol (1, 4-BG) or Ethylene Glycol (EG).
And the diphenylmethane diisocyanate in the component B is PM 200.
The preparation method of the polyurethane composite material for biodegradable packaging comprises the following steps:
(1) the component A comprises: stirring and mixing polycaprolactone A, polycaprolactone B, polylactic acid, a cross-linking agent, a chain extender, a foam stabilizer, a surfactant, water, a composite catalyst and an auxiliary agent in a mixing kettle at normal temperature, and discharging to obtain the polycaprolactone A-polycaprolactone B-based composite material;
(2) the component B is polyether polyol modified isocyanate, and the preparation method comprises the following steps:
firstly pumping diphenylmethane diisocyanate, controlling the temperature below 50 ℃, pumping polyether polyol with the temperature lower than 45 ℃ into a reaction kettle, stirring for 15 minutes, keeping the temperature at about 50 ℃, adding small molecular alcohol in batches, heating to 60-65 ℃ within 30 minutes, and keeping the temperature for 30 minutes; and when the content of NCO% reaches a set value, cooling to 10-30 ℃ to obtain the component B.
Wherein:
the mixing kettle in the step (1) is preferably a stainless steel mixing kettle; the stirring speed is 100-150 rpm, the preferred stirring speed is 120 rpm, and the stirring time is 0.5 hour.
The polyurethane composite material for biodegradable packaging is prepared by mixing biodegradable polyol polycaprolactone, polylactic acid, a cross-linking agent and a chain extender, wherein the raw materials are all polyols which are common in the market, and the polyol is matched with a catalyst and an auxiliary agent to prepare the composite material A. The polyurethane foam obtained by the reaction of the composite material A and the polyether polyol modified isocyanate B has certain openness, low density, large foaming ratio and small heat release amount in the reaction process, has a good filling effect on equipment and instruments, and has both mechanical strength and buffering performance.
The polyurethane foam prepared by the polyurethane composition material is environment-friendly, ester bonds in a skeleton structure can be decomposed into alcohol and carboxylic acid through hydrolysis, and carbamate bonds can be decomposed into carbamate and alcohol under hydrolysis. According to the phosphate buffer hydrolysis test method, the degradation rate of the polyurethane foam has a higher degradation rate than that of polyether polyurethane foam.
The biodegradable polyurethane material synthesized by the polyurethane composite material has biodegradability under the condition of ensuring excellent foam strength and mechanical property, the biodegradable polyurethane foam plastic can be quickly degraded by water and microorganisms after being buried, and the degradation product does not pollute the environment and soil.
Compared with the prior art, the invention has the following beneficial effects:
(1) the polyurethane foam prepared by the polyurethane composite material for biodegradable packaging has biodegradability, the packaging material can be biodegraded after being buried for 3-5 years after being used, and the decomposed organic matter is small in fragment and further decomposed into carbon dioxide and water, so that the environment-friendly effect is achieved.
(2) The polyurethane foam prepared by the polyurethane composite material for biodegradable packaging has certain porosity, low density, large foaming ratio and small heat release amount in the reaction process, has good filling effect on equipment and instruments, and has both mechanical strength and buffering performance.
(3) The biodegradable polyurethane composite material for packaging adopts water as a foaming agent, has zero Ozone Depletion Potential (ODP) and low Global Warming Potential (GWP), and has the characteristics of safety and environmental protection.
(4) The preparation method of the polyurethane composite material for biodegradable packaging meets the process requirements of manual operation and machine batch production of polyurethane foam, has high operability, and has good cushioning packaging effect on equipment and instruments with complex structures.
Drawings
FIG. 1 is a plot of weight loss of polyurethane foam.
Detailed Description
The present invention is further described below with reference to examples.
Example 1
The polyurethane composite material for biodegradable packaging described in this embodiment 1 is prepared from, by mass, 1: 1.0 of a component A and a component B, wherein:
the component A is prepared from the following raw materials in parts by mass:
wherein:
the polylactic acid (PLA) has a hydroxyl value of 240mgKOH/g, a functionality of 2, a viscosity of 6000mpa.s at 25 ℃ and a water content of less than 0.05 wt%.
The composite catalyst is formed by mixing N, N '-dimethylcyclohexylamine, N' -dimethylbenzylamine and bis (dimethylaminoethyl) ether.
The polyether polyol in the component B is INOVORL 330N.
The small molecular alcohol in the component B is 1, 4-butanediol.
And the diphenylmethane diisocyanate in the component B is PM 200.
The preparation method of the polyurethane composite material for biodegradable packaging in this embodiment 1 comprises the following steps:
the preparation method of the component A comprises the following steps: polycaprolactone A, polycaprolactone B, polylactic acid, a cross-linking agent, a chain extender, a foam stabilizer, a surfactant, water, a composite catalyst and an auxiliary agent are stirred and mixed in a mixing kettle at the temperature of 30 ℃, the mixture is stirred for 0.5 hour at the rotating speed of 120 revolutions per minute, and the mixture is discharged to serve as the component A.
The component B is polyether polyol modified isocyanate, and the preparation method comprises the following steps:
firstly pumping PM200, controlling the temperature below 50 ℃, pumping INOVORL 330N with the temperature lower than 45 ℃ into a reaction kettle, stirring for 15 minutes, keeping the temperature at about 50 ℃, adding 1, 4-butanediol in batches, heating to 62 ℃ within 30 minutes, and keeping the temperature for 30 minutes; and when the content of NCO% reaches a set value, cooling to 25 ℃ to obtain the component B.
The polyurethane foam is prepared from the biodegradable polyurethane composite material for packaging, wherein A, B components are mixed according to a mass ratio of 1: 1.0 at 22 ℃, stirring for 8s at the rotating speed of 3000r/min, placing in a square mold of 30cm x 10cm, setting the mold temperature at 45 ℃, opening the mold for 30min, and curing at room temperature for 72h to prepare the polyurethane foam A.
Example 2
The polyurethane composite material for biodegradable packaging described in this embodiment 2 is prepared from, by mass, 1:1.25 of a component a and a component B, wherein:
the component A is prepared from the following raw materials in parts by mass:
wherein:
the polylactic acid (PLA) has a hydroxyl value of 260mgKOH/g, a functionality of 2, a viscosity of 6800mpa.s at 25 ℃ and a moisture content of less than 0.05 wt%.
The composite catalyst is formed by mixing N, N '-dimethylcyclohexylamine, N' -dimethylbenzylamine and bis (dimethylaminoethyl) ether.
The polyether polyol in the component B is INOVORL 330N.
The small molecular alcohol in the component B is 1, 4-butanediol.
And the diphenylmethane diisocyanate in the component B is PM 200.
The preparation method of the polyurethane composite material for biodegradable packaging in this embodiment 2 comprises the following steps:
the preparation method of the component A comprises the following steps: polycaprolactone A, polycaprolactone B, polylactic acid, a cross-linking agent, a chain extender, a foam stabilizer, a surfactant, water, a composite catalyst and an auxiliary agent are stirred and mixed in a mixing kettle at the temperature of 30 ℃, the mixture is stirred for 0.5 hour at the rotating speed of 120 revolutions per minute, and the mixture is discharged to serve as the component A.
The component B is polyether polyol modified isocyanate, and the preparation method comprises the following steps:
firstly pumping PM200, controlling the temperature below 50 ℃, pumping INOVORL 330N with the temperature lower than 45 ℃ into a reaction kettle, stirring for 15 minutes, keeping the temperature at about 50 ℃, adding 1, 4-butanediol in batches, heating to 62 ℃ within 30 minutes, and keeping the temperature for 30 minutes; and when the content of NCO% reaches a set value, cooling to 25 ℃ to obtain the component B.
The polyurethane foam is prepared from the biodegradable polyurethane composite material for packaging, wherein A, B components are mixed according to a mass ratio of 1:1.25 at 22 ℃, stirring for 8s at the rotating speed of 3000r/min, placing in a square mold of 30cm x 10cm, setting the mold temperature at 45 ℃, opening the mold for 30min, and curing at room temperature for 72h to prepare the polyurethane foam B.
Example 3
The polyurethane composite material for biodegradable packaging described in this embodiment 3 is prepared from, by mass, 1: 1.5 of a component A and a component B, wherein:
the component A is prepared from the following raw materials in parts by mass:
wherein:
the polylactic acid (PLA) has a hydroxyl value of 280mgKOH/g, a functionality of 2, a viscosity of 7500mpa.s at 25 ℃ and a moisture content of less than 0.05 wt%.
The composite catalyst is formed by mixing N, N '-dimethylcyclohexylamine, N' -dimethylbenzylamine and bis (dimethylaminoethyl) ether.
The polyether polyol in the component B is INOVORL 330N.
The small molecular alcohol in the component B is 1, 4-butanediol.
And the diphenylmethane diisocyanate in the component B is PM 200.
The preparation method of the polyurethane composite material for biodegradable packaging in this embodiment 3 comprises the following steps:
the preparation method of the component A comprises the following steps: polycaprolactone A, polycaprolactone B, polylactic acid, a cross-linking agent, a chain extender, a foam stabilizer, a surfactant, water, a composite catalyst and an auxiliary agent are stirred and mixed in a mixing kettle at the temperature of 30 ℃, the mixture is stirred for 0.5 hour at the rotating speed of 120 revolutions per minute, and the mixture is discharged to serve as the component A.
The component B is polyether polyol modified isocyanate, and the preparation method comprises the following steps:
firstly pumping PM200, controlling the temperature below 50 ℃, pumping INOVORL 330N with the temperature lower than 45 ℃ into a reaction kettle, stirring for 15 minutes, keeping the temperature at about 50 ℃, adding 1, 4-butanediol in batches, heating to 62 ℃ within 30 minutes, and keeping the temperature for 30 minutes; and when the content of NCO% reaches a set value, cooling to 25 ℃ to obtain the component B.
The polyurethane foam is prepared from the biodegradable polyurethane composite material for packaging, wherein A, B components are mixed according to a mass ratio of 1: 1.5 at 22 ℃, stirring for 8s at the rotating speed of 3000r/min, placing in a square mold of 30cm x 10cm, setting the mold temperature at 45 ℃, opening the mold for 30min, curing at room temperature for 72h, and preparing the polyurethane foam C.
Comparative example 1
The polyurethane composite material described in comparative example 1 is prepared from the following components in a mass ratio of 1:1.25 of a component a and a component B, wherein:
the component A is prepared from the following raw materials in parts by mass:
wherein the polyether polyol INOVOL R4110 has a hydroxyl value of 420-.
The hydroxyl value of the polyether polyol INOVOL F330N is 32-36mgKOH/g, the viscosity at 25 ℃ is 800-1000 mpa.s, and the water content is less than 0.05 wt%.
The composite catalyst is formed by mixing N, N '-dimethylcyclohexylamine, N' -dimethylbenzylamine and bis (dimethylaminoethyl) ether.
The surfactant is NP-10, produced by Jilin northern Huifeng chemical company.
The preparation method of the component A comprises the following steps: polyether polyol INOVOL R4110, polyether polyol INOVOLF330N, foam stabilizer L-580, composite catalyst, water and NP-10 are stirred and mixed in a mixing kettle at 30 ℃, stirred for 0.5 hour at the rotating speed of 120R/min and discharged to serve as a component A.
The component B is isocyanate PM200 of Vanhua chemical Co.
A, B components are mixed at 22 ℃ according to the mass ratio of 1:1.25, stirred for 8s at the rotating speed of 3000r/min, placed in a square mold of 30cm x 10cm, the temperature of the square mold is set at 45 ℃, the mold is opened for 30min, and then the mixture is cured for 72h at room temperature, so that polyurethane foam D is prepared.
The polyurethane foams prepared in examples 1 to 3 and comparative example 1 were subjected to the performance test, and the test results are shown in Table 1.
TABLE 1 results of product Performance test obtained in examples 1 to 3 and comparative example 1
The degradation performance characterization of the prepared sample is carried out by adopting an outdoor soil burying degradation experimental method: the polyurethane foams prepared in examples 1 to 3 and comparative example 1 were numbered A to D and buried in the general horticultural soil at intervals of about 10cm, and were allowed to degrade under natural conditions. Taking out some polyurethane foam samples every 15 days, cleaning with deionized water, placing in a 50 ℃ forced air drying oven for 24h for drying, finally balancing for 24h under the normal temperature condition, measuring the weight loss rate of the foam, and plotting the relation of the weight loss rate to the time, as shown in figure 1. It can be seen from FIG. 1 that at 60 days, the weight loss ratios of the foams of Nos. A-C under natural conditions were 6.8%, 6.4% and 6.1%, respectively, while the weight loss ratio of the foam of comparative example D was only 0.65%. Therefore, the polyurethane foam prepared from the degradable combined polyether has better degradation performance in natural environment.
Claims (9)
1. A biodegradable polyurethane composite material for packaging is characterized in that: the mass ratio of 1: 1.0-1.5 of a component A and a component B, wherein:
the component A is prepared from the following raw materials in parts by mass:
the component B is prepared from the following raw materials in parts by mass:
10-20 parts of polyether polyol
2-5 parts of small molecular alcohol
60-85 parts of diphenylmethane diisocyanate.
2. The biodegradable polyurethane composite material for packaging according to claim 1, wherein: the hydroxyl value of polycaprolactone A is 320-560mgKOH/g, the functionality is 3, the viscosity at 30 ℃ is 400-850 mpa.s, and the water content is less than 0.05 wt%.
3. The biodegradable polyurethane composite material for packaging according to claim 1, wherein: the hydroxyl value of polycaprolactone B is 200-240mgKOH/g, the functionality is 2, the viscosity at 30 ℃ is 250-350 mpa.s, and the water content is less than 0.05 wt%.
4. The biodegradable polyurethane composite material for packaging according to claim 1, wherein: the polylactic acid has a hydroxyl value of 200-.
5. The biodegradable polyurethane composite material for packaging according to claim 1, wherein: the cross-linking agent is tri-functionality micromolecular alcohol; the chain extender is difunctional micromolecular alcohol; the foam stabilizer is polysiloxane-oxyalkylene block copolymer.
6. The biodegradable polyurethane composite material for packaging according to claim 1, wherein: the surfactant is a silicone surfactant; the composite catalyst is a mixture of N, N '-dimethylcyclohexylamine, N' -dimethylbenzylamine and bis (dimethylaminoethyl) ether; the auxiliary agent is a diluent, and the diluent is propylene carbonate.
7. The biodegradable polyurethane composite material for packaging according to claim 1, wherein: the polyether polyol in the component B is INOVORL 330N; the small molecular alcohol is one of 1, 4-butanediol or ethylene glycol; diphenylmethane diisocyanate was PM 200.
8. The method for preparing the polyurethane composite material for biodegradable packaging as set forth in claim 1, wherein:
the component A comprises: stirring and mixing polycaprolactone A, polycaprolactone B, polylactic acid, a cross-linking agent, a chain extender, a foam stabilizer, a surfactant, water, a composite catalyst and an auxiliary agent in a mixing kettle at normal temperature, and discharging to obtain the polycaprolactone A-polycaprolactone B-based composite material;
and B component: firstly pumping in diphenylmethane diisocyanate, controlling the temperature to be below 50 ℃, pumping polyether polyol with the temperature lower than 45 ℃ into a reaction kettle, maintaining the temperature at 50 ℃, adding small molecular alcohol in batches, heating to 60-65 ℃ within 30 minutes, and keeping the temperature for 30 minutes; and when the content of NCO% reaches a set value, cooling to 10-30 ℃ to obtain the component B.
9. The method for preparing the polyurethane composite material for biodegradable packaging as set forth in claim 8, wherein: in the step (1), the stirring speed is 100-150 rpm, and the stirring time is 0.5 hour.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112011030A (en) * | 2020-08-31 | 2020-12-01 | 荆晓东 | Polylactic acid polyurethane material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112011030A (en) * | 2020-08-31 | 2020-12-01 | 荆晓东 | Polylactic acid polyurethane material and preparation method thereof |
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Application publication date: 20200331 |