CN1546574A - Polyfoam using plant fiber as material and its preparation method - Google Patents
Polyfoam using plant fiber as material and its preparation method Download PDFInfo
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- CN1546574A CN1546574A CNA2003101124588A CN200310112458A CN1546574A CN 1546574 A CN1546574 A CN 1546574A CN A2003101124588 A CNA2003101124588 A CN A2003101124588A CN 200310112458 A CN200310112458 A CN 200310112458A CN 1546574 A CN1546574 A CN 1546574A
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- 239000000835 fiber Substances 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000000463 material Substances 0.000 title claims abstract description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000005855 radiation Effects 0.000 claims abstract description 14
- 230000005251 gamma ray Effects 0.000 claims abstract description 6
- 238000005187 foaming Methods 0.000 claims abstract description 4
- 235000013311 vegetables Nutrition 0.000 claims description 67
- 239000004033 plastic Substances 0.000 claims description 29
- 229920003023 plastic Polymers 0.000 claims description 29
- 239000000843 powder Substances 0.000 claims description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 241000196324 Embryophyta Species 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 239000002023 wood Substances 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 14
- 238000002203 pretreatment Methods 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 8
- 238000007278 cyanoethylation reaction Methods 0.000 claims description 8
- 239000012978 lignocellulosic material Substances 0.000 claims description 8
- 229920003987 resole Polymers 0.000 claims description 8
- 235000011150 stannous chloride Nutrition 0.000 claims description 8
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000004821 distillation Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000006260 foam Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 244000198134 Agave sisalana Species 0.000 claims description 3
- 235000011624 Agave sisalana Nutrition 0.000 claims description 3
- 244000099147 Ananas comosus Species 0.000 claims description 3
- 235000007119 Ananas comosus Nutrition 0.000 claims description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 3
- 240000008564 Boehmeria nivea Species 0.000 claims description 3
- 244000025254 Cannabis sativa Species 0.000 claims description 3
- 235000012766 Cannabis sativa ssp. sativa var. sativa Nutrition 0.000 claims description 3
- 235000012765 Cannabis sativa ssp. sativa var. spontanea Nutrition 0.000 claims description 3
- 244000060011 Cocos nucifera Species 0.000 claims description 3
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 3
- 240000000491 Corchorus aestuans Species 0.000 claims description 3
- 235000011777 Corchorus aestuans Nutrition 0.000 claims description 3
- 235000010862 Corchorus capsularis Nutrition 0.000 claims description 3
- 235000004431 Linum usitatissimum Nutrition 0.000 claims description 3
- 240000006240 Linum usitatissimum Species 0.000 claims description 3
- 229920001219 Polysorbate 40 Polymers 0.000 claims description 3
- 235000009120 camo Nutrition 0.000 claims description 3
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- 239000011487 hemp Substances 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- 235000010483 polyoxyethylene sorbitan monopalmitate Nutrition 0.000 claims description 3
- 239000000249 polyoxyethylene sorbitan monopalmitate Substances 0.000 claims description 3
- 229940101027 polysorbate 40 Drugs 0.000 claims description 3
- 239000012745 toughening agent Substances 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 229920001214 Polysorbate 60 Polymers 0.000 claims description 2
- 239000003377 acid catalyst Substances 0.000 claims description 2
- 239000013543 active substance Substances 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
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- 235000010989 polyoxyethylene sorbitan monostearate Nutrition 0.000 claims description 2
- 239000001818 polyoxyethylene sorbitan monostearate Substances 0.000 claims description 2
- 229940113124 polysorbate 60 Drugs 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 241001133760 Acoelorraphe Species 0.000 claims 2
- 238000000034 method Methods 0.000 abstract description 11
- 229920001342 Bakelite® Polymers 0.000 abstract 1
- 239000004637 bakelite Substances 0.000 abstract 1
- 235000019256 formaldehyde Nutrition 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 23
- 235000011613 Pinus brutia Nutrition 0.000 description 23
- 241000018646 Pinus brutia Species 0.000 description 23
- 239000002689 soil Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
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- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
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- 235000013305 food Nutrition 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- OQUKIQWCVTZJAF-UHFFFAOYSA-N phenol;sulfuric acid Chemical compound OS(O)(=O)=O.OC1=CC=CC=C1 OQUKIQWCVTZJAF-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a polyfoam using plant fiber as material wherein its preparation method comprises reacting liquefied plant fiber with methyl aldehyde, creating bakelite an and foaming, the process for preparing liquefied plant fiber includes pre-treating through ultraviolet radiation and gamma-ray irradiation, then liquefied plant fiber is obtained by oxybenzene dissolving method.
Description
Technical field
The present invention relates to a kind of is raw material, biodegradable foam plastic and preparation method thereof with the natural plant fibre.
Background technology
Porous plastics is important packing and material of construction, has been widely used in every field such as food, electrical equipment, furniture, household.But with synthetic resins is the various porous plastics of raw material, is difficult to degraded under field conditions (factors), thereby has increased environmental pressure, be known as " white pollution ".In order to address this problem, utilize the degradability of vegetable fibre, the preparation porous plastics is one of alternative method.In order to reach this purpose, the liquefaction of vegetable fibre is at first to need the problem that solves.
Vegetable fibre is that nature is contained very abundant reproducible natural composite material, and owing to increasingly sharpening of energy dilemma and environmental pollution, the utilization fully rationally of vegetable fibre just becomes more urgent.But because structural complicacy of vegetable fibre and singularity make its application at chemical industry and energy field have bigger difficulty.Early stage research lays particular emphasis on the method for utilization pyrolytic decomposition or high-pressure liquefaction, makes vegetable fibre liquefaction, and product is separated to be used respectively, can develop hydrocarbon fuel and chemical feedstocks.The liquefaction reaction condition of these class methods is comparatively harsh, and practicality is relatively poor.People wished to keep its polymer characteristics when vegetable fibre is liquefied afterwards, thereby can utilize the structure and the performance of vegetable fibre, but not the vegetable fibre degraded is degraded worker's raw material.This class liquifying method, the condition that original adoption is comparatively violent under high temperature (more than 250 ℃), high pressure, catalyst-free condition, is dissolved in vegetable fibre the method for some organic solvent.Progressively changed low temperature in the employing (80-150 ℃) afterwards into, normal pressure has under the condition of catalyzer and carries out dissolution with solvents, with some chemical modifications of utilizing vegetable fibre often, as fat modification or the etherification modified liquefaction efficiency of strengthening.Yet the chemical modification of vegetable fibre can improve the liquefaction cost, and can increase environmental pressure, and is improper economically.For this reason, should adopt the means of vegetable fibre direct liquefaction as far as possible, or by the simple physics treatment process, to increase the efficient of liquefaction.
Summary of the invention
The purpose of this invention is to provide a kind of porous plastics with environmental protection characteristic and preparation method thereof, this method cost is low, and the porous plastics of preparation can be applicable to packaging industry, has biological degradability, can alleviate the pollution to environment.
Porous plastics of the present invention is to be raw material with the liquefaction vegetable fibre, is toughener with the vegetable fibre, and the weight percent of each component is: liquefaction vegetable fibre 30-60%, the short fiber 20-40% that cuts plant, formaldehyde 20-40%.This porous plastics can be applicable to packaging industry, has biological degradability.
As the weak point of the toughener fiber that cuts plant is in jute, flax, sisal hemp, ramie, hemp, Exocarpium cocois (Cocos nucifera L) and the pineapple leaves one or more.And the raw material of liquefaction vegetable fibre mainly is all kinds of wood powders, also can be the powder of other vegetable fibre.
The preparation method of above porous plastics is divided into following step:
1), preparation liquefaction vegetable fibre: earlier the former vegetable fibre of powdery is sieved in (40 order); In reactor, add phenol and catalyzer, adding through radiation pre-treatment main component after the heating and melting is the powdery plant fiber of various wood powders, the weight ratio of phenol and vegetable fibre is 1～5, the adding mode of powdery plant fiber is divided into disposable or muptiple-use adding, backflow stirring reaction 90min in 150 ℃ oil bath; Catalyzer is the composition of following material, amount with respect to vegetable fibre is calculated: sulfuric acid 0-3%, p-methyl benzenesulfonic acid 0-7%, tin protochloride 0-1%, crystal aluminum chloride 0-1%, after reaction finished, system was cooled to 60 ℃, add methyl alcohol dilution liquefaction vegetable fibre, separable liquefaction vegetable fibre of suction filtration and residue; Use the methanol wash liquefied residue, wash residue again with water, vacuum-drying residue part is weighed; Filtrate is partly carried out underpressure distillation, and the vegetable fibre that will liquefy separates with methyl alcohol, the Methanol Recovery utilization, and the vacuum-drying of liquefaction vegetable fibre, for future use;
2), preparation lignocellulosic material base resole: the phenol hydroxyl value of at first measuring the liquefaction vegetable fibre by standard method; Phenol hydroxyl value by liquefaction wood converses phenol: formaldehyde=1: 1.6, and the NaOH consumption accounts for 1% of phenol; With aforementioned proportion liquefaction wood, formaldehyde, NaOH in reactor, in 85 ℃ bath heating reflux reaction 4-5 hour; Being reacted to viscosity is stopped reaction behind 2～10Pa.S, adds hydrochloric acid and is adjusted to neutrality, and underpressure distillation is removed unnecessary water to water-content and is about 6% after the cooling, lignocellulosic material base resole;
3), mixed foaming: get lignocellulosic material base resole and place paper or plastic containers for 100 parts, even with the weak point of the weight percent 20-40% blending in of fibers that cuts plant, add 10～20phr, weight ratio subsequently and be 1: 1 acid catalyst phosphoric acid and sulfuric acid or sulfuric acid and sulfonic acid, add 3～5phr tensio-active agent polysorbate40 or polysorbate60, add 10～20phr ether and make whipping agent, under room temperature, stir fast and foam, put into slaking 10～30min in 60～65 ℃ the baking oven afterwards.
In the preparation process of liquefaction vegetable fibre, the radiation pre-treatment can utilize uviolizing to handle the former vegetable fibre of powdery; The power of ultraviolet lamp is: 1～5kw, the distance between powdery plant fiber and ultraviolet lamp is: 20～50cm, irradiation time is: 10～30 hours.
In the preparation process of liquefaction vegetable fibre, the radiation pre-treatment can also utilize gamma-rays, uviolizing to handle the former vegetable fibre of powdery; Gamma-ray irradiation dosage is 1～5Mrad; Through the powdery plant fiber of radiation treatment, available ultraviolet ray is further handled, and the power of ultraviolet lamp is: 1～5kw, the distance between powdery plant fiber and ultraviolet lamp is: 20～50cm, irradiation time is: 5～30 hours.
In the preparation process of liquefaction vegetable fibre, the radiation pre-treatment is to utilize uviolizing to handle the cyanoethylation modified plant fibers of weightening finish 20～40%; The power of ultraviolet lamp is: 1～5kw, the distance between powdery plant fiber and ultraviolet lamp is: 20～50cm, irradiation time is: 5～30 hours.
Experiment shows that through the vegetable fibre of radiation treatment, required liquefaction condition greatly reduces, and can improve its liquefaction efficiency.But there are many reactive behavior points in the vegetable fibre after the liquefaction on chemical structure, for its next step resinifying utilization provides condition.Simultaneously, the liquefaction vegetable fibre has also kept the original structure of vegetable fibre to a certain extent, thereby gives the biological degradability of final material.Utilization is that the resin of raw material can be made tackiness agent with the liquefaction vegetable fibre, foam material, and can be applicable to the aspects such as matrix of fibre composite.Adopt the inventive method to prepare porous plastics efficient height, cost is low, and its product can be applicable to packaging industry, has biological degradability, can alleviate the pollution to environment.
Embodiment
The invention will be further described below in conjunction with specific embodiment.
Embodiment 1-5
Preparation process is:
1), preparation liquefaction vegetable fibre:
Raw material: 40 order pine powders, phenol is made solvent.Temperature of reaction: 150 ℃, the reaction times: 90min.Feed way: disposable adding or be divided into twice adding (add 2/3 earlier, add 1/3 again), liquefaction reaction the results are shown in Table 1.The metal chlorate is a permeate agent, can strengthen the diffusion of phenol in vegetable fibre, improves the reaction probability.Add pine powder in batches, the ratio of solvent in the initial reaction stage system is improved, help vegetable fibre liquefaction.
2), preparation wood fibre based resole:
Getting each example liquefaction pine is raw material, after the phenol hydroxyl value of mensuration liquefaction wood, and phenol: formaldehyde=1: 1.6; Catalyst n aOH consumption accounts for 1% of phenol.Take by weighing above-mentioned liquefaction wood in proportion, formaldehyde, NaOH are in reactor, and stopped reaction behind 85 ℃ of following back flow reaction 4h adds hydrochloric acid and regulates about pH=7, and unnecessary water is removed in underpressure distillation after the cooling.Under the normal temperature, the finished product viscosity is about 8Pa.S.
3), mixed foaming:
The wood fibre based resole that takes by weighing 100 parts mixes with a certain proportion of weak point fiber (20phr) that cuts plant in paper or plastic containers.Add 5phr sulfuric acid and 5phr sulfonic acid, add the 3phr polysorbate40, add ether whipping agent (10phr) again, under room temperature, stir fast, behind 30～60S, bubble, put into slaking 10min in the baking oven about 60 ℃ afterwards.Foam density is about 50kg/m
3
4) degradation experiment of porous plastics: (10 * 10 * 10cm) soil bury, and take out after 1 year, measure rate of weight loss (seeing Table 1) with the porous plastics monoblock.In addition, porous plastics is clayed into power, soil buries after 3 years and checks, basic degraded finishes.
The degradation property embodiment 1～5 of former efflorescence liquefaction of table 1 pine and porous plastics thereof
| Embodiment | Wood/phenol | Sulfuric acid (%) | P-methyl benzenesulfonic acid (%) | Tin protochloride (SnCl 2.2H 2O ????，％) | Aluminum chloride (AlCl 3.6H 2O， ???％) | Residue rate (%) | Whole soil buries rate of weight loss (%) after 1 year |
| ????1 | ????0.5 | 1 | 5 | ???1 | ??32 | ??35 | |
| ????2 | ????0.5 | 1 | 5 | ????1 | ??22 | ??32 | |
| ????3 | ????0.75 | 7 | ????1 | ??41 | ??28 | ||
| ????4 | ????1 | 7 | ????1 | ??62 | ??23 | ||
| ????5 a | ????1 | 7 | ????1 | ??49 | ??21 |
aAnnotate: pine powder is divided into twice adding (add 2/3 earlier, add 1/3 again)
Embodiment 6～9
The preparation method is identical with embodiment 1-5.But former vegetable fibre utilizes the ultraviolet lamp of different capacity the vegetable fibre powder to be carried out the ultraviolet irradiation pre-treatment of different time earlier before liquefaction.Concrete grammar is raw material: 40 order pine powders, phenol is made solvent, pine powder/phenol=1.During UV treatment, the distance between pine powder and ultraviolet lamp is: 20cm; Temperature of reaction: 100 ℃, the reaction times: 90min; Catalyzer is: 1% sulfuric acid, 5% p-methyl benzenesulfonic acid, 1% tin protochloride; The adding mode of pine powder: disposable adding; Liquefaction reaction the results are shown in Table 2.UV-irradiation may be accelerated the degraded of xylogen, thereby improves the liquefaction performance of vegetable fibre.Can also see that from table 2 with the increasing of ultraviolet lamp tube power, the liquefaction performance of pine improves.Corresponding to the liquefaction wood of preparation after handling through the 5000W uv light irradiation, the biological degradability of prepared porous plastics is also listed in table 2.
Table 2 ultraviolet irradiation is handled the degradation property embodiment 6～9 of former efflorescence liquefaction of pine and porous plastics thereof
| Embodiment | Irradiation time (h) | Ultra-violet lamp tube power (W) | Whole soil buries rate of weight loss (%) after 1 year | ||
| 1000(I) | ??2000(II) | ??5000(III) | |||
| Residue rate (%) | |||||
| 6 | ??0 | ????60 | ????60 | ????60 | ????23 |
| 7 | ??10 | ????52 | ????47 | ????45 | ????28 |
| 8 | ??20 | ????43 | ????38 | ????35 | ????33 |
| 9 | ??30 | ????40 | ????25 | ????20 | ????35 |
Embodiment 10-11
The preparation method is identical with embodiment 1-5.But former vegetable fibre carries out gamma-rays or gamma-rays earlier in conjunction with the former vegetable fibre of ultraviolet irradiation pre-treatment before liquefaction.Concrete grammar is raw material: 40 order pine powders, phenol is made solvent, pine powder/phenol=1.After pine powder carried out the various dose gamma-ray irradiation respectively, use the 2000W ultra violet lamp again, the distance between pine powder and ultraviolet lamp is: 20cm, irradiation time 10 hours; Temperature of reaction: 100 ℃, the reaction times: 90min; Catalyzer is: 1% sulfuric acid, 5% p-methyl benzenesulfonic acid, 1% tin protochloride; The adding mode of pine powder: disposable adding; Concrete reaction result sees Table 3.Pine powder is through Co
60Behind the irradiation, the chemical structure of its lignocellulosic material can change, and high-energy radiation can destroy cellulosic crystalline texture in the lignocellulosic material, and cellulosic response capacity is improved, but meanwhile, Co
60Radiation that xylogen in the vegetable fibre is taken place is crosslinked, this effect can reduce the liquefaction performance of vegetable fibre.Therefore, irradiation dose can not be too high.If elder generation then can avoid the generation of above-mentioned phenomenon, and play the effect of tangible promotion vegetable fibre liquefaction through gamma-rays, again with the ultraviolet irradiation processing.For the liquefaction wood through making behind the 5Mrad gamma-ray irradiation, the biological degradability of prepared porous plastics is also listed in table 3.
Table 3 gamma-rays, ultraviolet irradiation ultraviolet irradiation are handled the former efflorescence liquefaction of pine
And the degradation property embodiment 10～11 of porous plastics
| Embodiment | Radiation mode | Gamma-ray irradiation dosage (Mrad) | Whole soil buries rate of weight loss (%) after 1 year | ||
| ????1(I) | ????3(II) | ????5(III) | |||
| Residue rate (%) | |||||
| 10 | Gamma-rays | ????60 | ????40 | ????30 | 30 |
| 11 | Gamma-rays+ultraviolet ray | ????32 | ????20 | ????15 | 37 |
Embodiment 12～14
The preparation method is identical with embodiment 1-5.But vegetable fibre is the modification of process cyanoethylation before liquefaction, and utilizes ultraviolet ray to carry out pre-irradiation and handle.Concrete grammar is raw material: the cyanoethylation pine powder, and weightening finish 20%, phenol is made solvent, wood powder/phenol=1.With the ultra violet lamp of 2000W 20 hours, the distance between wood powder and ultraviolet lamp was: 20cm; Temperature of reaction: 100 ℃, the reaction times: 90min; Catalyzer is: 10% hydrochloric acid, or 7% p-methyl benzenesulfonic acid, 1% tin protochloride; The adding mode of wood powder: disposable adding; Concrete reaction result sees Table 4.As seen, UV-irradiation can further promote the phenolysis of chemical modification wood powder, thereby makes simple chemical modification method (cyanoethylation) practical more.For catalyzer is p-methyl benzenesulfonic acid (7%), and during tin protochloride (1%), the biological degradability behind the wooden one-tenth porous plastics of prepared liquefaction is also listed in table 4.
Table 4 ultraviolet irradiation is handled cyanoethylation pine powder chemistry liquefaction embodiment 12～14
| Embodiment | The wood fibre type | Catalyst type | Whole soil buries rate of weight loss (%) after 1 year | |
| ?HCl(10％) ?(I) | P-methyl benzenesulfonic acid (7%), tin protochloride (1%) (II) | |||
| Residue rate (%) | ||||
| 12 | Former pine powder | ?66 | ????70 | ????23 |
| 13 | The cyanoethylation pine powder | ?48 | ????50 | ????25 |
| 14 | Ultraviolet irradiation cyanoethylation pine powder | ?20 | ????25 | ????33 |
Claims (6)
1, a kind of porous plastics is characterized in that with the liquefaction vegetable fibre be raw material, is toughener with the vegetable fibre, and the weight percent of each component is: liquefaction vegetable fibre 30-60%, the short fiber 20-40% that cuts plant, formaldehyde 20-40%.
2, a kind of porous plastics as claimed in claim 1, it is characterized in that the short fiber that cuts plant is one or more in jute, flax, sisal hemp, ramie, hemp, palm, Exocarpium cocois (Cocos nucifera L) and the pineapple leaves, the raw material of liquefaction vegetable fibre mainly is all kinds of wood powders, can be the powder of other vegetable fibre also, comprise jute, flax, sisal hemp, ramie, hemp, palm, Exocarpium cocois (Cocos nucifera L) and pineapple leaves.
3, a kind of preparation method of porous plastics as claimed in claim 1 or 2 is characterized in that this preparation method's step is:
1), preparation liquefaction vegetable fibre: in reactor, add phenol and catalyzer, adding through radiation pre-treatment, main component after the heating and melting is the powdery plant fiber of various wood powders, the weight ratio of phenol and vegetable fibre is 1～5, the adding mode of powdery plant fiber is divided into disposable or muptiple-use adding, in 150 (oil bath in backflow stirring reaction 90min; Catalyzer is the composition of following material, amount with respect to vegetable fibre is calculated: sulfuric acid 0-3%, p-methyl benzenesulfonic acid 0-7%, tin protochloride 0-1%, crystal aluminum chloride 0-1%, after reaction finished, system was cooled to 60 ℃, add methyl alcohol dilution liquefaction vegetable fibre, separable liquefaction vegetable fibre of suction filtration and residue; Use the methanol wash liquefied residue, wash residue again with water, vacuum-drying residue part is weighed; Filtrate is partly carried out underpressure distillation, and the vegetable fibre that will liquefy separates with methyl alcohol, the Methanol Recovery utilization, and the vacuum-drying of liquefaction vegetable fibre, for future use;
2), preparation lignocellulosic material base resole: the phenol that converts by the phenol hydroxyl value of liquefaction wood: formaldehyde=1: 1.6, the NaOH consumption accounts for 1% of phenol; Take by weighing a certain amount of above-mentioned liquefaction wood, formaldehyde, NaOH in reactor, in 85 ℃ bath heating reflux reaction 4-5 hour; Being reacted to viscosity is stopped reaction behind 2～10Pa.S, adds hydrochloric acid and is adjusted to neutrality, and underpressure distillation is removed unnecessary water to water-content and is about 6% after the cooling, lignocellulosic material base resole;
3), mixed foaming: get 100 parts of lignocellulosic material base resoles, place paper or plastic containers, even with the weak point of the weight percent 20-40% blending in of fibers that cuts plant, add 10～20phr, weight ratio subsequently and be 1: 1 acid catalyst phosphoric acid and sulfuric acid or sulfuric acid and sulfonic acid, add 3～5phr tensio-active agent polysorbate40 or polysorbate60, add 10～20phr ether and make whipping agent, under room temperature, stir fast and foam, put into slaking 10～30min in 60～65 ℃ the baking oven afterwards.
4, a kind of preparation method of porous plastics as claimed in claim 3 is characterized in that the radiation pre-treatment in the preparation process of liquefaction vegetable fibre is to utilize uviolizing to handle the former vegetable fibre of powdery; The power of ultraviolet lamp is: 1～5kw, the distance between powdery plant fiber and ultraviolet lamp is: 20～50cm, irradiation time is: 10～30 hours.
5, a kind of preparation method of porous plastics as claimed in claim 3 is characterized in that the radiation pre-treatment in the preparation process of liquefaction vegetable fibre is to utilize gamma-rays, uviolizing to handle the former vegetable fibre of powdery; Gamma-ray irradiation dosage is 1～5Mrad; Through the powdery plant fiber of radiation treatment, available ultraviolet ray is further handled, and the power of ultraviolet lamp is: 1～5kw, the distance between powdery plant fiber and ultraviolet lamp is: 20～50cm, irradiation time is: 5～30 hours.
6, a kind of preparation method of porous plastics as claimed in claim 3 is characterized in that the radiation pre-treatment in the preparation process of liquefaction vegetable fibre is to utilize uviolizing to handle the cyanoethylation modified plant fibers of weightening finish 20～40%; The power of ultraviolet lamp is: 1～5kw, the distance between powdery plant fiber and ultraviolet lamp is: 20～50cm, irradiation time is: 5～30 hours.
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| CNA2003101124588A CN1546574A (en) | 2003-12-05 | 2003-12-05 | Polyfoam using plant fiber as material and its preparation method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102061059A (en) * | 2010-12-22 | 2011-05-18 | 中国林业科学研究院林产化学工业研究所 | Wood fiber reinforced inflaming retarding foam material and machining method thereof |
| CN102532442A (en) * | 2011-12-26 | 2012-07-04 | 浙江省林业科学研究院 | Preparation method of bamboo wood phenolic alcohol liquefaction product formaldehyde resin for foaming |
| CN103289310A (en) * | 2013-06-13 | 2013-09-11 | 北京林业大学 | Wood liquefied substance foamed material and preparation method thereof |
-
2003
- 2003-12-05 CN CNA2003101124588A patent/CN1546574A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102061059A (en) * | 2010-12-22 | 2011-05-18 | 中国林业科学研究院林产化学工业研究所 | Wood fiber reinforced inflaming retarding foam material and machining method thereof |
| CN102061059B (en) * | 2010-12-22 | 2012-07-25 | 中国林业科学研究院林产化学工业研究所 | Wood fiber reinforced inflaming retarding foam material and machining method thereof |
| CN102532442A (en) * | 2011-12-26 | 2012-07-04 | 浙江省林业科学研究院 | Preparation method of bamboo wood phenolic alcohol liquefaction product formaldehyde resin for foaming |
| CN103289310A (en) * | 2013-06-13 | 2013-09-11 | 北京林业大学 | Wood liquefied substance foamed material and preparation method thereof |
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