CN102276971B - Fully-degradable polymethyl methacrylate ethylene carbonic ester foaming material and preparation method thereof - Google Patents
Fully-degradable polymethyl methacrylate ethylene carbonic ester foaming material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a fully-degradable polymethyl methacrylate ethylene carbonic ester foaming material and a preparation method thereof. The fully-degradable polymethyl methacrylate ethylene carbonic ester foaming material is composed of the following components in parts by weight: 100 parts of polymethyl methacrylate ethylene carbonic ester, 5-100 parts of starch, 5-20 parts of water and 1-10 parts of nucleating agent. In the fully-degradable polymethyl methacrylate ethylene carbonic ester foaming material, the starch is added in the polymethyl methacrylate ethylene carbonic ester, thereby improving the thermostability and mechanical performance of the foaming material, and substantially lowering the production cost. Compared with the material performance of petroleum bases, such aspolyethylene, polypropylene and the like, the polymethyl methacrylate ethylene carbonic ester has better affinity, the prepared foaming material has a better abscess structure, and the foaming multiplying power is higher. In the fully-degradable polymethyl methacrylate ethylene carbonic ester foaming material, no organic foaming agent is used, so that the obtained foaming material has high foaming multiplying power, can be completely degraded, the technology is simple, the production process is safe and environmentally-friendly, and the cost can be greatly lowered. The foaming material is safe to environment, does not pollute the environment and can be used in various fields by replacing petroleum base foaming materials.
Description
Technical field
The present invention relates to a kind of fully degradation polymethylethylene carbonic ester ester foaming material and preparation method thereof.
Background technology
Compared with pure plastics, foamed plastics has a series of features such as density is small, specific strength is high, energy absorption capability is strong, sound isolating and heat insulating performance is good, is applied widely in fields such as transportation and packing, military project, Aero-Space, commodity.Realizing the foamed plastics of industrialized production has polystyrene (PS), polyethylene (PE), polyurethane (P U R), polypropylene（PP), ethylene-vinyl acetate copolymer（EVA) etc..But they belong to petroleum-based plastics, degradation property is poor, and has respective limitation.Wherein PE, EVA foaming material performance are preferable, but expansion ratio is relatively low, and PU expanded material expansion ratios are higher, but easily fall the foam bits of static electrification, are easily drawn into when making packaging material and are caused to use failure inside packaging material.As commodity logistics, electronics and information industry are continued to develop, the consumption of bubble wrap product is increasing rapidly, so as to accelerate the depletion rate of this non-renewable resources of oil, face the predicament of increasingly depleted；And discarded object of this non-degradable bubble wrap product after brings serious negative effect to environment, exacerbates white pollution.On the other hand, the burning and industrial processes of fossil fuel cause carbon dioxide content in air increasingly to increase, and " greenhouse effects " phenomenon is increasingly serious.The recycling of carbon dioxide is also the field that whole world scientist all the time compares concern.
Lined polymethyl ethylene carbonate not only make use of carbon dioxide, and Wholly-degradable, be the environment-friendly environment-friendly materials of a class.Compared with above oil based foam material, the existing higher expansion ratio of lined polymethyl ethylene carbonate based foam material solves PS etc. and easily falls the problem of electrostatic foam is considered to be worth doing again.At present, the research of lined polymethyl ethylene carbonate expanded material has obtained certain progress.In this experimental group patent（ ZL200510033659.8）A kind of method for manufacturing lined polymethyl ethylene carbonate expanded material is invented, i.e., using lined polymethyl ethylene carbonate as matrix, to add CBA, blowing promotor and processing aid, stir mixing, through banburying, again in double screw extruder, drying tunnel is sent into, is foamed through plastifying fusion.The technology is simple, but is due to that simple lined polymethyl ethylene carbonate foaming material performance has certain limitation, somewhat limited in widely using.In China Patent No.（ZL200510100342.1）Disclose a kind of fully degradation polymethylethylene carbonic ester ester/vinyl-vinyl alcohol copolymer composite foam material and preparation method thereof.This method is that first lined polymethyl ethylene carbonate and ethylene-vinyl alcohol copolymer are blended, then is blended with foaming agent, nucleator and auxiliary agent, and finally by extrusion, molding and calendering process foam in a heated condition.Because ethylene-vinyl alcohol copolymer price is higher, material preparation process is relatively complicated, and with the addition of some auxiliary agents etc., will all increase cost, unfavorable for producing sale in enormous quantities.The relatively inexpensive degradable polymer material of other prices is added in lined polymethyl ethylene carbonate resin blending and modifying is carried out to it, not only increase the heat endurance and mechanical performance of expanded material, and production cost can also be greatly lowered, it is the effective ways for optimizing lined polymethyl ethylene carbonate foaming.
Conventional foaming technique has physical blowing and chemical blowing at present, and wherein chemical blowing purposes is wider.CBA and some auxiliary agents etc. are mainly added in polymer by it, decompose produce N at high temperature2, CO2Deng realizing the foaming of polymer.In foaming process, the CBA used, which decomposes the solid deposits produced and the foaming agent not decomposed completely, still certain harm to environment, it is impossible to which comply fully with environmental protection crosses range request.The freon used in physical blowing, supercritical CO2Deng having certain harm pollution to air, butane, the inflammability of the low boiling organic foaming agent such as pentane also limit its extensive use.In Chinese patent（Publication number CN 101519504A and publication number CN 101492547A) disclose a kind of foaming agent that made of water and prepare PP, the method for PE expanded materials.But due to PP, PE hydrophily extreme differences, compatibility is bad, and the expanded material expansion ratio prepared is relatively low.
The content of the invention
The purpose of the present invention is to overcome the deficiencies in the prior art there is provided a kind of fully degradation polymethylethylene carbonic ester ester foaming material using water as foaming agent and preparation method thereof.
The present invention using by carbon dioxide and epoxypropane copolymerization into Wholly-degradable lined polymethyl ethylene carbonate as matrix, water is used as foaming agent, carrier and blending and modifying agent of the starch as water are selected, lined polymethyl ethylene carbonate/starch foaming material is prepared using the method directly extruded.
The purpose of the present invention is to be achieved through the following technical solutions：
A kind of fully degradation polymethylethylene carbonic ester ester foaming material, is made up of the component of following parts by weight：
100 parts of lined polymethyl ethylene carbonate,
5-100 parts of starch,
5-20 parts of water,
1-10 parts of nucleator.
In above-mentioned fully degradation polymethylethylene carbonic ester ester foaming material, the lined polymethyl ethylene carbonate is the super high molecular weight product obtained by carbon dioxide and propylene oxide copolymer, and its number-average molecular weight is 50,000 to 500,000, and chemical constitution is：
Wherein n is 490-5000.
In above-mentioned fully degradation polymethylethylene carbonic ester ester foaming material, the starch is cornstarch, potato starch, wheaten starch, one or more of mixtures in tapioca.
In above-mentioned fully degradation polymethylethylene carbonic ester ester foaming material, the nucleator is talcum powder, calcium carbonate, montmorillonite, clay, one or more kinds of mixtures in silica or titanium dioxide.
The preparation method of above-mentioned fully degradation polymethylethylene carbonic ester ester foaming material, comprises the following steps：By each group
Divide uniform in stirrer for mixing, the direct extrusion foaming in single screw rod or double screw extruder；Extrusion foaming system temperature interval is：
Single screw rod：150-190 DEG C of blending temperature, exports die head temperature：120-160℃；
Twin-screw：Blending temperature：140-190 DEG C, export die head temperature：120-160℃；
It is greater than 0.5MPa with outlet pressure difference in screw rod.By control water evaporation and screw rod inside and outside pressure differential obtain a kind of high foamability Wholly-degradable lined polymethyl ethylene carbonate composite foam material of water as foaming agent, mainly for the manufacture of vibration-absorptive material, heat preserving and insulating material, package packing supplies, degradable foamed sheet material, food pallet or Related product.
Compared with prior art, the present invention has the advantages that：
The degradable composite foam material of the present invention using by carbon dioxide and epoxypropane copolymerization into Wholly-degradable lined polymethyl ethylene carbonate as matrix, water is used as foaming agent, select carrier and blending and modifying agent of the starch as water, using the method directly extruded, by control water evaporation and screw rod inside and outside pressure differential prepare lined polymethyl ethylene carbonate/starch foaming material.Starch is added in lined polymethyl ethylene carbonate resin and not only increases the heat endurance and mechanical performance of expanded material, and production cost can also be greatly lowered.With the petroleum based material ratio such as polyethylene, polypropylene, lined polymethyl ethylene carbonate has more preferable affinity with water, and obtained expanded material has the foam structure changed, and expansion ratio is higher.Without using organic foaming agent in the present invention, obtained expanded material expansion ratio is high, Wholly-degradable, and technique is simple, and production process safety and environmental protection can substantially reduce cost.The expanded material is environmentally safe pollution-free, can be used in instead of oil based foam material in each field.
Embodiment
Below the present invention is further described with embodiment.
Embodiment 1.
Each component is weighed by following parts by weight：100 parts of lined polymethyl ethylene carbonate, 20 parts of cornstarch, 5 parts of water, 1 part of talcum powder.First water is well mixed with starch, then above-mentioned raw material are stirred in mixer, is directly extruded in single screw rod, extrusion foaming system temperature interval is：One area：50 DEG C, 2nd area：160 DEG C, 3rd area：170 DEG C, die head：130℃；Rotating speed, 30rpm；Obtain lined polymethyl ethylene carbonate/starch foaming material that a kind of water is prepared as foaming agent.Expansion ratio is 20 times of foamed plastics.
Embodiment 2.
Each component is weighed by following parts by weight：100 parts of lined polymethyl ethylene carbonate, 30 parts of cornstarch, 10 parts of water, 2 parts of talcum powder.First water is well mixed with starch, then above-mentioned raw material are stirred in mixer, is directly extruded in single screw rod, extrusion foaming system temperature interval is：One area：50 DEG C, 2nd area：160 DEG C, 3rd area：170 DEG C, die head：140℃；Rotating speed, 30rpm obtains lined polymethyl ethylene carbonate/starch foaming material that a kind of water is prepared as foaming agent.Expansion ratio is 24 times of foamed plastics.
Embodiment 3.
Each component is weighed by following parts by weight：100 parts of lined polymethyl ethylene carbonate, 40 parts of cornstarch, 15 parts of water, 3 parts of montmorillonite.First water is well mixed with starch, then above-mentioned raw material are stirred in mixer, is directly extruded in single screw rod, extrusion foaming system temperature interval is：One area：50 DEG C, 2nd area：170 DEG C, 3rd area：170 DEG C, die head：140℃；Rotating speed, 40rpm obtains lined polymethyl ethylene carbonate/starch foaming material that a kind of water is prepared as foaming agent.Expansion ratio is 32 times of foamed plastics.
Embodiment 4.
Each component is weighed by following parts by weight：100 parts of lined polymethyl ethylene carbonate, 30 parts of wheaten starch, 9 parts of water, 1 part of titanium dioxide.First water is well mixed with starch, then above-mentioned raw material are stirred in mixer, is directly extruded in single screw rod, extrusion foaming system temperature interval is：One area：90 DEG C, 2nd area：170 DEG C, 3rd area：180 DEG C, die head：150℃；Rotating speed, 40rpm obtains lined polymethyl ethylene carbonate/starch foaming material that a kind of water is prepared as foaming agent.Expansion ratio is 21 times of foamed plastics.
Embodiment 5.
Each component is weighed by following parts by weight：100 parts of lined polymethyl ethylene carbonate, 40 parts of wheaten starch, 15 parts of water, 3 parts of silica.First water is well mixed with starch, then above-mentioned raw material are stirred in mixer, is directly extruded on twin-screw, extrusion foaming system temperature interval is：One area：50 DEG C, 2nd area：130 DEG C, 3rd area：170 DEG C, 4th area：180 DEG C, 5th area：180 DEG C, 6th area：170 DEG C, 7th area：160 DEG C, die head：150℃；Rotating speed, 50rpm obtains lined polymethyl ethylene carbonate/starch foaming material that a kind of water is prepared as foaming agent.Expansion ratio is 17 times of foamed plastics.
Embodiment 6.
Each component is weighed by following parts by weight：100 parts of lined polymethyl ethylene carbonate, 50 parts of cornstarch, 20 parts of water, 4 parts of titanium dioxide.First water is well mixed with starch, then above-mentioned raw material are stirred in mixer, is directly extruded on twin-screw, extrusion foaming system temperature interval is：One area：70 DEG C, 2nd area：140 DEG C, 3rd area：160 DEG C, 4th area：170 DEG C, 5th area：170 DEG C, 6th area：170 DEG C, 7th area：160 DEG C, die head：140℃；Rotating speed, 40rpm obtains lined polymethyl ethylene carbonate/starch foaming material that a kind of water is prepared as foaming agent.Expansion ratio is 35 times of foamed plastics.
Embodiment 7.
Each component is weighed by following parts by weight：100 parts of lined polymethyl ethylene carbonate, 40 parts of wheaten starch, 15 parts of water, 2 parts of talcum powder.First water is well mixed with starch, then above-mentioned raw material are stirred in mixer, is directly extruded on twin-screw, extrusion foaming system temperature interval is：One area：90 DEG C, 2nd area：140 DEG C, 3rd area：170 DEG C, 4th area：180 DEG C, 5th area：180 DEG C, 6th area：170 DEG C, 7th area：160 DEG C, die head：150℃；Rotating speed, 40rpm obtains lined polymethyl ethylene carbonate/starch foaming material that a kind of water is prepared as foaming agent.Expansion ratio is 26 times of foamed plastics.
Experiment condition is as described above, the experimental formula and result of above example are as shown in table 1.
Table 1：Lined polymethyl ethylene carbonate/starch foaming material raw material components（Parts by weight）And expansion ratio
| Embodiment | 1 | 2 | 3 | 4 | 5 | 6 | 7 |
| PPC (parts by weight） | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| Cornstarch（Parts by weight） | 20 | 30 | 40 |
 |
50 |
 |
|
| Wheaten starch（Parts by weight） | 30 | 40 | 40 | ||||
| Water（Parts by weight） | 5 | 10 | 15 | 9 | 15 | 20 | 15 |
| Talcum powder（Parts by weight） | 1 | 2 | 2 | ||||
| Montmorillonite（Parts by weight） |
 |
 |
3 |
 |
 |
 |
 |
| Silica（Parts by weight） | 3 | ||||||
| Titanium dioxide（Parts by weight） |
 |
 |
 |
1 |
 |
4 |
 |
| Expansion ratio | 20 | 24 | 32 | 21 | 17 | 35 | 26 |
Claims (3)
1. a kind of preparation method of fully degradation polymethylethylene carbonic ester ester foaming material, it is characterised in that,Comprise the following steps：
（1）It is by following parts by weight that each component is uniform in stirrer for mixing, wherein,
100 parts of lined polymethyl ethylene carbonate,
5-100 parts of starch,
5-20 parts of water,
1-10 parts of nucleator；
（2）The direct extrusion foaming in single screw rod or double screw extruder, extrusion foaming system temperature interval is：
Single screw rod：150-190 DEG C of blending temperature, exports die head temperature：120-160℃；
Twin-screw：Blending temperature：140-190 DEG C, export die head temperature：120-160℃；
It is greater than 0.5MPa with outlet pressure difference in screw rod；
Step（1）The nucleator is talcum powder, montmorillonite, clay, one or more kinds of mixtures in titanium dioxide.
2. the preparation method of fully degradation polymethylethylene carbonic ester ester foaming material according to claim 1, it is characterized in that, the lined polymethyl ethylene carbonate is the super high molecular weight product obtained by carbon dioxide and propylene oxide copolymer, its number-average molecular weight is 50,000 to 500,000, chemical constitution is：
Wherein n is 490-5000.
3. the preparation method of fully degradation polymethylethylene carbonic ester ester foaming material according to claim 1, it is characterised in that the starch is cornstarch, potato starch, wheaten starch, one or more of mixtures in tapioca.
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| CN102796361A (en) * | 2012-08-10 | 2012-11-28 | 中国科学院长春应用化学研究所 | Biodegradable carbon dioxide-epoxypropane copolymer foamed plastic and preparation method thereof |
| CN105968767B (en) * | 2016-06-03 | 2017-10-17 | 中山大学 | A kind of lined polymethyl ethylene carbonate expanded material and preparation method thereof |
| CN108164959B (en) * | 2017-12-27 | 2020-04-17 | 中国科学院长春应用化学研究所 | Halogen-free flame-retardant polypropylene carbonate foam material and preparation method and application thereof |
| CN109553810A (en) * | 2018-12-10 | 2019-04-02 | 王泽宝 | A kind of environment-friendly type buffer and its preparation process |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100999602A (en) * | 2006-12-18 | 2007-07-18 | 中山大学 | Degradable carbon dioxide plastic base composite material and preparation process thereof |
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| CN100999602A (en) * | 2006-12-18 | 2007-07-18 | 中山大学 | Degradable carbon dioxide plastic base composite material and preparation process thereof |
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| Title |
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| 汪树生等.水发泡淀粉挤出泡沫的结构与性能.《应用化学》.2010,第27卷(第7期),759-763. * |
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