CN1149594A - Preparing regenerated cellulose water-proof film by using bagasse and wheat-straw pulp - Google Patents
Preparing regenerated cellulose water-proof film by using bagasse and wheat-straw pulp Download PDFInfo
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- CN1149594A CN1149594A CN 95118161 CN95118161A CN1149594A CN 1149594 A CN1149594 A CN 1149594A CN 95118161 CN95118161 CN 95118161 CN 95118161 A CN95118161 A CN 95118161A CN 1149594 A CN1149594 A CN 1149594A
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Abstract
The present invention discloses a kind of method to prepare regenerated cellulose water proof film by using bagasse pulp and wheat-straw pulp two kinds of raw material. The regenerated cellulose film prepared by cuprammonia method is firstly undergone plasticizing and drying then coated on two sides with the mixture of degradable low mole-cular weight polyurethane and unsaturated polyester, the water proof film is obtained after solidifying and crosslinking. The waterproof property of said film is good, after soaking in water for 1 hr, its strength still retains over 85%, the percentage of contraction after soaking in water for 24 hr and drying is within 4%, the permeability amount of vapour is lower than 0.01 (g/cm2.day). Said film can be substituted for non gradable plastic film used in the place where the requirement of bio-degradability is very high, such as ground film, planting film and bag for raising seedlings.
Description
The invention discloses a class and utilize bagasse and straw pulp to prepare the method for regenerative cellulose waterproof film, it belongs to technical field of polymer chemistry, also belongs to the coatings chemistry technical field, and its international Patent classificating number is respectively C08 and C09.
The annual production of the various products of synthetic macromolecule is above 100,000,000 tons in the world.These with the petroleum products be the macromolecular material of raw material not only because of being difficult to the natural degradation contaminate environment, and face exhausted day by day petroleum resources, its raw material is subjected to serious prestige rib.At one of countermeasure of above problem is to research and develop natural macromolecular material energetically.Mierocrystalline cellulose is the abundantest natural polymer, but for protecting forest resources, the wood-cellulose exploitation is subjected to certain limitation.For this reason, the cellulose slurry of development and use agricultural wastes bagasse and straw production prepares the biological degradability regenerative cellulose film, and so not only abundant raw material, inexpensive is beneficial to and saves limited petroleum resources, and can protect environment.
In recent years, the new development of the research and development of relevant degradability cellulose membrane mainly contains Mierocrystalline cellulose/chitosan complex film (flat 2-127486 of JP; " Ind.Eng.Chem.Res. " 1991,30,788); Mierocrystalline cellulose/polyurethane mixture film (Eur.Pat.EP447041); Poly(lactic acid) coating waterproof paper (the flat 4-334448 of JP); Mierocrystalline cellulose-vulcabond graft copolymer (" J.Macromol.Chem. " 1981, A16,473) etc.Before, the patent of invention of our application disclosed with cuprammonium process and has prepared regenerated cellulose film and handle the method (CN1061608.A that makes the water resisting property film with dilution tung oil; 88103036.8).
The objective of the invention is: utilize two kinds of feedstock production regenerated cellulose films of bagasse pulp and straw pulp, and adopt the low molecular weight polyurethane and the unsaturated polyester compo of degradability to make it water-repellancy, dimensional stability and the intensity of curing cross-linked with further raising film in the film two sided coatings.
For realizing that the technical measures that the object of the invention is taked are: the alpha-cellulose content of used bagasse and two kinds of slurries of straw is respectively 83% and 72%, and viscosity-average molecular weight Mn is 12.6 * 10
4With 11.1 * 10
4Prepare water white regenerated cellulose film by above-mentioned disclosed cuprammonium process, remake WATER REPELLENT through plasticising, after drying.With tolylene diisocyanate and Viscotrol C or TriMethylolPropane(TMP) is synthetic gives polymers, again it is mixed by suitable weight ratio with acrylic styrene copolymer and dilute 5～15 times with ethyl acetate, add 0.1%N then, the N-dimethylethanolamine.This compo is evenly coated in the regenerated cellulose film two sides, and baking can obtain waterproof membrane by curing cross-linked in 2～5 minutes under 80 ℃.Polyurethane water-proof layer weight accounts for 10～15% of cellulose membrane.
Gordian technique of the present invention is the viscosity controller that urethane gives polymers, gives the composition proportioning and the control of solidification value and time of polymers and unsaturated polyester (acrylic styrene copolymer).Above factor is to the density of polyurethane water-proof layer and it produces hydrogen bond with the cellulose membrane surface and chemical bond has engaged crucial influence.
The present invention has substantive different compared to the prior art, and marked improvement is arranged.The present invention utilizes bagasse pulp to be raw material cuprammonium process preparation, regeneration cellulose membrane first.Giving polymers and acrylate-vinylbenzene multiple copolymer with urethane mixes and as WATER REPELLENT the water-repellancy of film and film that dimensional stability is handled than dilution tung oil is significantly improved to regenerated cellulose film.The film that film water vapour infiltration capacity of the present invention (P) and immersion back dimensional contraction rate (St) are all handled than tung oil reduces over half, and it improves about 20% to soak the caudacoria strength ratio in water.Because the urethane and the unsaturated polyester of lower molecular weight have biodegradable (" polymer " [day], 1990,39,280), and they only account for fully biodegradable regenerated cellulose film 10～15%, therefore film of the present invention still can keep good biodegradability.Such film is embedded in the soil to be fallen by microbiological degradation, and is pollution-free to soil, ocean and atmosphere.Think that thus they can replace the nondegradation plastic film and be used for the crucial occasion of those biodegradabilities, for example mulch film, plant film, Seedling bag etc.In addition, the used thinner of the present invention is an ethyl acetate, and it is nontoxic and can be by evaporation, condensation and recycling use.
The subordinate list explanation:
Table 1 is a waterproof membrane and without the tensile strength (σ of WATER REPELLENT film
b), the comparison of water vapor permeable amount (P) and shrinking percentage (St).
Embodiment 1:
Prepare regenerated cellulose film by cuprammonium process, behind 5% glycerine plasticising 10min, be attached to dry on the sheet glass stand-by.The preparation method that urethane gives polymers is as follows: purified and dry Viscotrol C and the 59g tolylene diisocyanate of crossing of 100g placed flask, at room temperature stir 1h and promptly obtain giving polymers, sealing is preserved.The preparation method of unsaturated polyester is: place flask to be heated to boiling the 55g ethyl acetate, stir adding BPO down, and slow dropwise addition of acrylic acid ester-vinylbenzene mix monomer (methyl methacrylate: butyl acrylate: vinylformic acid: vinylbenzene=1: 3: 0.3: 1) be total to 54g.Widely different again stream 3h after dripping in 3h, it is 30%～40% that adding ethyl acetate in cooling back makes the coating solid content.1g is given after the acrylic styrene copolymer of polymers, 1g 35% and the commercially available S01-17 liquid of 1g places beaker to stir,, add 0.1%N then, the N-dimethylethanolamine with the dilution of 12g ethyl acetate.Immediately this compo is evenly coated in the regenerated cellulose film two sides, baking can make water white waterproof membrane by curing cross-linked in about 5 minutes under 80 ℃.This film and the tensile strength σ that does not make the film that the film of WATER REPELLENT, rare tung oil handle
b(under dry state and the warm attitude), the shrinking percentage St that water vapor permeable amount P and film soaked after drying in 24 hours again all lists in table 1.
Embodiment 2:
The preparation method of regenerated cellulose film and acrylic styrene copolymer is same as embodiment 1.The preparation method that urethane gives polymers is as follows: TriMethylolPropane(TMP) and the 150g pimelinketone of 30g after dehydration placed the 500ml there-necked flask, stirring at room temperature makes it to dissolve fully, slowly is added drop-wise to the 116g tolylene diisocyanate in this solution again and controls its temperature keeping 1h below 40 ℃.Be heated to 60 ℃ of reaction 2h then, 85～90 ℃ of reactions promptly made in 5 hours gives polymers.5g is given polymers, and 1g 35% acrylic styrene copolymer solution and 1.5g polyether glycol place beaker to stir the back with the dilution of 40g ethyl acetate, add 0.1%N then, the N-dimethylethanolamine.This compo is evenly coated in the regenerated cellulose film two sides immediately, and drying by the fire 2～3min down at 80 ℃ is that curing cross-linked makes water white waterproof membrane.Every performance index of this film and untreated film are all listed in table 1.The result illustrates film of the present invention and has excellent water-resistance, and soaks its tensile strength of back and still keep more than 85% in water, and shrinking percentage reduces to below 4%, and the water vapor permeable amount is at 0.01 (g/cm
2Day) in.
Table 1 waterproof membrane and handle the tensile strength of film without WATER REPELLENT film, rare tung oil
(σ
b), water vapor permeable amount (P) and shrinking percentage (St)
| The examination film | Raw material and treatment process | ?σ b(kg/cm 2) | ??????P (g/cm 2·day) | ??St ?(％) | ||
| Do | Wet | |||||
| The WATER REPELLENT film | ?1 ?2 ?3 | Straw pulp, bagasse pulp of the present invention, cotton linter pulp of the present invention, rare tung oil | ??349 ??400 ??312 | ??305 ??387 ??200 | ????0.008 ????0.010 ????0.020 | ??3.7 ??3.5 ??8.0 |
| Untreated film | ?1 ? ?2 | The straw pulp bagasse pulp | ??334 ? ??361 | ??121 ? ??132 | ????0.029 ? ????0.028 | ??11 ? ??10 |
Claims (4)
1. method of utilizing bagasse and straw pulp to prepare regenerative cellulose waterproof film, it is characterized in that: the present invention presses cuprammonium process preparation, regeneration cellulose membrane with bagasse pulp and straw pulp first, film gives with urethane after polymers and acrylate-vinylbenzene multiple copolymer compo makes WATER REPELLENT to regenerated cellulose film through plasticising, dry back, the waterproof membrane that acquisition has excellent water-resistance;
2. described by claim 1 is that raw material prepares regenerative cellulose waterproof film by cuprammonium process with bagasse pulp and straw pulp, and it is characterized in that: the alpha-cellulose content of two kinds of raw materials that the present invention is used is respectively 83% and 72%, and viscosity-average molecular weight is 12.6 * 10
4With 11.1 * 10
4
3. described by claim 1 is that raw material prepares regenerative cellulose waterproof film by cuprammonium process with bagasse pulp and straw pulp, it is characterized in that: it is 7: 3～8: 2 by the weight ratio that TriMethylolPropane(TMP) and tolylene diisocyanate synthetic urethane give polymers and acrylic styrene copolymer that urethane gives polymers and acrylic styrene copolymer compo carry out WATER REPELLENT to regenerated cellulose film prescription; The weight ratio of being given polymers and acrylic styrene copolymer by Viscotrol C and tolylene diisocyanate synthetic urethane is 9: 1～10: 1, adds 20% left and right sides polyether glycol, makes the waterproof membrane very strong with the Mierocrystalline cellulose bonding force;
4. prepare regenerative cellulose waterproof film with bagasse pulp and straw pulp by cuprammonium process by claim 1 is described, it is characterized in that: the regenerated cellulose film WATER REPELLENT is to adopt to add N, behind the N-dimethylethanolamine, the compo that urethane gives polymers and acrylic styrene copolymer can solidify rapidly on the cellulose membrane surface, and be 2～5min (under 80 ℃) its set time.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95118161A CN1059682C (en) | 1995-11-07 | 1995-11-07 | Preparing regenerated cellulose water-proof film by using bagasse and wheat-straw pulp |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95118161A CN1059682C (en) | 1995-11-07 | 1995-11-07 | Preparing regenerated cellulose water-proof film by using bagasse and wheat-straw pulp |
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| Publication Number | Publication Date |
|---|---|
| CN1149594A true CN1149594A (en) | 1997-05-14 |
| CN1059682C CN1059682C (en) | 2000-12-20 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN95118161A Expired - Fee Related CN1059682C (en) | 1995-11-07 | 1995-11-07 | Preparing regenerated cellulose water-proof film by using bagasse and wheat-straw pulp |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105566502A (en) * | 2015-12-21 | 2016-05-11 | 同济大学 | Preparation method of waterproof renewable nano cellulose thin film |
| CN105820376A (en) * | 2016-03-17 | 2016-08-03 | 莫海尼·M·塞恩 | Heatproof flexible nano-composite sheet and preparation method thereof |
| CN107125061A (en) * | 2016-12-05 | 2017-09-05 | 广东乐将生物科技有限公司 | A kind of degradable mulch for coating waterproof layer |
| CN111321631A (en) * | 2020-03-02 | 2020-06-23 | 东莞协旺彩印有限公司 | Waterproof paper box and preparation process thereof |
| CN114957964A (en) * | 2022-06-17 | 2022-08-30 | 宋伟杰 | Degradable automobile foot mat material and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1061608A (en) * | 1990-11-17 | 1992-06-03 | 武汉大学 | Cotton stalk and Pericarppium arachidis hypogaeae prepare the method for regenerated cellulose film |
| CN1036140C (en) * | 1992-12-18 | 1997-10-15 | 中国国际科技促进会 | Plant cellulose film product and preparation process thereof |
| CN1110287A (en) * | 1994-04-09 | 1995-10-18 | 中国国际科技促进会 | Reinforcing degradable plant cellulose products |
-
1995
- 1995-11-07 CN CN95118161A patent/CN1059682C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105566502A (en) * | 2015-12-21 | 2016-05-11 | 同济大学 | Preparation method of waterproof renewable nano cellulose thin film |
| CN105566502B (en) * | 2015-12-21 | 2018-06-26 | 同济大学 | The preparation method of the renewable nano-cellulose film of water resistance |
| CN105820376A (en) * | 2016-03-17 | 2016-08-03 | 莫海尼·M·塞恩 | Heatproof flexible nano-composite sheet and preparation method thereof |
| CN107125061A (en) * | 2016-12-05 | 2017-09-05 | 广东乐将生物科技有限公司 | A kind of degradable mulch for coating waterproof layer |
| CN111321631A (en) * | 2020-03-02 | 2020-06-23 | 东莞协旺彩印有限公司 | Waterproof paper box and preparation process thereof |
| CN114957964A (en) * | 2022-06-17 | 2022-08-30 | 宋伟杰 | Degradable automobile foot mat material and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1059682C (en) | 2000-12-20 |
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