CN1043143A - The manufacture method of Dropless high polymer - Google Patents
The manufacture method of Dropless high polymer Download PDFInfo
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- CN1043143A CN1043143A CN89104723A CN89104723A CN1043143A CN 1043143 A CN1043143 A CN 1043143A CN 89104723 A CN89104723 A CN 89104723A CN 89104723 A CN89104723 A CN 89104723A CN 1043143 A CN1043143 A CN 1043143A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/25—Greenhouse technology, e.g. cooling systems therefor
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Abstract
The present invention relates to a kind of manufacture method of Dropless high polymer.Macromolecule membrane is carried out surface treatment, water-soluble monomer or water-soluble polymer and linking agent are dissolved in the solvent, make solution and be coated on the above-mentioned film, use uviolizing again.The water-absorbent film that makes has improved the shortcoming of intrinsic rerum natura, do not reduce mechanical property again simultaneously, and it is simple to have method for making, and cost is low, the productivity advantages of higher.
Description
The invention relates to the manufacture method of Dropless high polymer.
The macromolecule membrane of polyolefine system is used as agricultural film and wrapping material, and they have favorable mechanical performance, optical property, nontoxicity and snappiness, thereby are widely used.But when these films used in the occasion that has large quantity of moisture, its surface had hydrophobicity, and this character is extremely harmful.Specifically, when on agricultural, being used for simple and easy hot house, hydrogenesis in the hot house is on the internal surface of greenhouse, the transparency of film significantly descends, cause the efficient in the minimizing of sunlight transit dose, vegetable crop reduction, prolongation in vegetative period, greenhouse to reduce, in addition, the agglomerative water droplet is fallen and is taken in simple greenhouse sometimes, can make it barren even withered.Have again, because the hydrophobicity on surface is insecure even coated with hydrophobic printing ink or gelatin also adhere to.In addition, when the packaging material for food, the agglomerative water droplet causes the food sex change, when serious even addle.
In order to overcome above-mentioned shortcoming, people have developed some method of modifying.Wherein first method is to use PVA (PVOH) FILM, and the shortcoming of this method is, the water tolerance of these films own is relatively poor, and its treatment process difficulty is big, and can not life-time service.Second method is a spraying special surface promoting agent on film, this method is to utilize the hydrophilic surface activity of special surface promoting agent, but when reality is used, attached to part on the film surface and water droplet generation emulsification, no condensed water drops runs off easily, in addition, the thickness that contains above-mentioned no condensed water drops layer is less, water-retaining capacity is limited, and weather resistance is poor.Therefore, though its initial stage effect is pretty good, persistence is very poor.The third method is the film of impregnation of fibers prime system resin in alkali lye, makes the cellulosefilm possess hydrophilic property, and this method causes the physical strength of film own significantly to descend owing to introducing hydrophilic group, this drawbacks limit its application.The 4th kind of method is that no condensed water drops such as stearic acid, lauric acid and macromolecule membrane (for example polyethylene film, polyvinyl chloride film) is mixing, this method is because used resin is poor with the consistency of no condensed water drops, dissolving is separated out on the surface of film, mist to occur white, it is opaque that film becomes, so that it is inhomogeneous that sunlight sees through, and the effect that was intended to the no condensing water droplet that reaches has not originally existed.
If these methods are used, then can avoid taking place above-mentioned defective to a certain extent, but the necessary possess hydrophilic property of this no condensed water drops, if it is present on the surface of film, then separated out by the water droplet dissolving, cause the performance of noncondensing water droplet to reduce, it is white to reappear mist.That is to say, do not have in this mixed type under the situation of condensing water droplet film, it is white to supervene mist, the performance of its noncondensing water droplet can only continue 20-45 days usually, because the speed that no condensed water drops discharges is very responsive to environment on every side, therefore it is real no condensing water droplet macromolecule membrane hardly.
In order to overcome above-mentioned contradiction, people develop the agricultural film of chemical modification.
So-called chemical modification method is to utilize radioactive rays, plasma body and ultraviolet ray to make water-soluble or the macromolecular grafted method that is aggregated on the film of water-swellable.Wherein, utilize the treatment process of radioactive rays and plasma body, obvious processing effect, and have multifarious advantage, but need the initial stage facility investment expense of great number, in addition, this method is unsuitable for producing in enormous quantities continuously, therefore also is difficult to practicability at present.Compare with Plasma Polymerization with above-mentioned radioactive rays, utilize ultraviolet graft polymerization method very easy, be used to improve purposes such as printability and tackiness effectively.Yet, there are some problems in method in the past aspect working continuously, for polyethylene film, ultraviolet irradiation time is more than 20 minutes, and must in nitrogen gas stream, react, through the macromolecule membrane of such graft reaction, when being used for the agricultural film of the no condensing water droplet of conduct, for the poor durability of water droplet, sunlight and other envrionment conditions, these are its fatal shortcomings.
Problem in view of the above, the inventor adopts following method to make to have fabulous absorptive macromolecule membrane:
Adopt corona discharge, acid treatment and flame treating etc. that macromolecule membrane is given processing, make it to give the active site that first generation can be carried out graft polymerization easily, then, use up and light trigger makes the water-soluble monomer graft polymerization, carry out crosslinking reaction simultaneously.Be characterized in suitably utilizing crosslinked bonded water-soluble monomer and high molecular characteristic, in addition, can continuous production, facility investment is cheap, manufacture method is simple and easy to do, be semipermanent or permanent for the weather resistance of water droplet, sunlight and surrounding environment.
Can be used for macromolecule membrane of the present invention, be to give through Corona discharge Treatment etc. handling the back in case the atomic group that just can generate by illumination can to begin to carry out graft polymerization, ion etc., can initiation grafting polymeric polymer, comprise polystyrene, polypropylene, polyethylene, poly--4-methyl-1-pentene, polymethylmethacrylate, polymeric amide-6, polyprene etc.
Light source adopts the light source that can produce 200-700nm, for example: lonely light modulation, Cooper-Hewitt lamp, high pressure mercury vapour lamp, xenon lamp, fluorescent lamp, metal halide lamp, tengsten lamp, sunlight etc., such light source can make light trigger decompose, and produces atomic group, ion isoreactivity point.The ideal irradiation time is 0.1-24 hour.
Giving film comprises with absorptive water-soluble or water-swellable monomer: vinylformic acid, N-vinyl pyrrolidone, methacrylic acid, acrylamide, Methacrylamide, 2-hydroxyethyl meth acrylate etc.; Water-soluble polymer can use single polymers that is made of above-mentioned water-soluble monomer and the multipolymer that is made of monomer more than two kinds.
Light trigger can use benzophenone, isopropyl diphenyl base ethanol ether ketone, benzoyl peroxide, N, N '-Diisopropyl azodicarboxylate etc.
Be used to dissolve water-soluble monomer, water-soluble polymer, light trigger and linking agent and photosensitizers equal solvent, can use methyl alcohol, ethanol, acetone, water, nucleic acid, ethyl methyl ketone and above-mentioned an amount of mixed solution more than two kinds.The photopolymerization solution that water-soluble monomer, initiator, water-soluble polymer, linking agent and photosensitizers etc. are mixed is coated on the macromolecule membrane equably, gives its wetting ability, makes and produces c=o functional group and c=c functional group on the macromolecule membrane.In order to make it to become the active site of graft reaction, this is swift in response carries out, must carry out Corona discharge Treatment, gas phase treatment, liquid phase processing etc. and give processing.Corona discharge is to adopt spark gap formula or electron tubes type to handle macromolecule membrane; It is with a kind of processing the in sulphuric acid soln, bichromate solutions, potassium permanganate solution and the surface water solution that liquid phase chemical is handled; Gas phase treatment can adopt any treatment process in spark processing, ozonize, oxygen processing, chlorine processing, sulphurous acid gas processing, the nitric acid gas processing.In addition, can carry out surface treatment with ultraviolet ray.
In order to increase high molecular weather resistance and physical strength, adjusting water ratio and swelling capacity, make it to carry out crosslinked combination through graft polymerization.Linking agent be polyfunctional acrylate, for example trimethylolpropane trimethacrylate (TMPTMA), tri methylol triacrylate (TMPTA) three vinylformic acid Ji Wusi (alcohol) esters (PETA) and above-mentioned more than two kinds mixture or their derivative.
Be used to make oxygen blocking in the photopolymerization solution through uviolizing, carry out the photosensitizers of the oxygen in the polymerization tank of graft polymerization, use one or two or more kinds the mixture in n-Butyl Amine 99, N-butylamine, triethylamine, diethylin ethyl-methyl acrylate, Triethylenetetramine (TETA), diethanolamine, thanomin, trolamine, the tribenzylamine.
In the present invention, for the absorptive weather resistance of testing the process surface treatment, giving absorptive macromolecule membrane, as shown in Figure 1, with the water-absorbent adhesion of film on the full surface of polyvinyl chloride pipe, be placed on average sunshine time and test, detect by an unaided eye in the field more than 10-12 hour.
The manufacture method of absorbent polymer film proposed by the invention is a kind of new method, because with chemically combined water-soluble or the character that the water-swellable polymer is had of macromolecule membrane, make water-absorbent can for good and all keep substantially, improve the shortcoming of intrinsic rerum natura, do not reduced mechanical property simultaneously again.In addition, this manufacture method is very easy, has the very high advantage of low cost of manufacture, productivity.
Fig. 1 is the synoptic diagram of experimental installation, and wherein A is treated film, and B is that diameter is the round shape pvc pipe of 90mm.
Narrate embodiment and comparative example below, but the present invention is not limited by these embodiment.
Embodiment 1
Is that 12 microns pet film carries out the surface and adds water decomposition and handle with the 15%NaOH aqueous solution to thickness, then, 150g vinylformic acid, 42g N-vinyl pyrrolidone, 50g benzophenone, 5g trimethylolpropane trimethacrylate (linking agent) and 59g diethanolamine (photosensitizers) are dissolved in the 720g normal hexane equably, are modulated into photopolymerization solution.Above film,, 5 80W/cm high pressure mercury vapour lamps are set continuously as light source with the interval of 20cm apart from the height of film 20cm.The above-mentioned photopolymerization solution of coating 3-5 micron thickness on film, and then under 50 ℃ ± 5 ℃, with 10-12 rice/minute speed with above-mentioned light source irradiation film, make the surface of film have water-absorbent.
Test-results is as shown in table 1.
Embodiment 2
42g acrylamide, 3g benzophenone, 10g three vinylformic acid Ji Wusi (alcohol) esters (pentaerythritoltriacrylate) and 2g thanomin are dissolved in the 500g acetone equably, are modulated into photopolymerization solution.
The polyethylene film that thickness is 30 microns, give processing with the corona discharge handler by the speed of 200W output rating and 5 meters/minute, apply the above-mentioned photopolymerization solution of 2-5 micron thickness then with pickling process, and then under 50 ℃ ± 5 ℃, with 10-15 rice/minute speed to the surface irradiation ultraviolet ray of above-mentioned film, make it surface modification.
Test-results is as shown in table 1.
Embodiment 3
100g vinylformic acid, 50g acrylamide and 10g benzophenone, 5g trolamine and 5g trimethylolpropane trimethacrylate are sneaked in the 500g ethyl methyl ketone equably, be modulated into photopolymerization solution.
The polyvinyl chloride film that thickness is 50 microns is used concentrated nitric acid gas processing 10 minutes, washes its surface then with water, and back to be dried applies above-mentioned photopolymerization solution with pickling process, then to its Continuous irradiation ultraviolet ray, makes it surface modification.
Test-results is as shown in table 1.
Embodiment 4
42g methacrylic acid, 30gN-vinyl pyrrolidone, 25g polyvinylpyrrolidone, 5gN-butylamine, 18g isopropyl diphenyl base ethanol ether ketone and 10g tri methylol triacrylate are dissolved in the 600g acetone, are modulated into photopolymerization solution.
The polymeric amide that thickness is 40 microns-6 film carries out same processing according to embodiment 2, applies the above-mentioned photopolymerization solution of 5 micron thickness then.To its irradiation ultraviolet radiation continuously, test-results is as shown in table 1 under 50 ℃ ± 5 ℃, with 10 meters/minute speed.
Embodiment 5
With the 5g thanomin, mixed dissolution is modulated into photopolymerization solution in 600g acetone equably with 180g acrylamide, 2g polyacrylamide, 30g phenyl methyl ketone, 10g three vinylformic acid Ji Wusi (alcohol) esters and 5g benzoyl peroxide.
The polyethylene film that thickness is 50 microns, carry out same processing by embodiment 2, apply above-mentioned photopolymerization solution equably with pickling process then, under 60 ℃-75 ℃, with 10-12 rice/minute speed to coated film irradiation ultraviolet radiation continuously.
Test-results is as shown in table 1.
Embodiment 6
50g vinylformic acid, 2g polyacrylic acid, 30gN-vinyl pyrrolidone, 3g poly-N-vinyl pyrrolidone, 20g benzophenone, 10g thanomin (photosensitizers) and 15g trimethylolpropane trimethacrylate are dissolved in the 500g acetone equably, are modulated into photopolymerization solution.
Thick 15 microns polypropylene film carries out same processing by embodiment 2, then with the above-mentioned photopolymerization solution of pickling process coating 3-5 micron, and then under 50 ℃ ± 5 ℃, with 10-15 rice/minute the speed irradiation ultraviolet radiation, make it surface modification.
Test-results is as shown in table 1.
Embodiment 7
54g Methacrylamide, 130g2-hydroxyethyl meth acrylate, 15g triethylamine and 10g trimethylolpropane trimethacrylate are sneaked in the 580g ethanol equably, be modulated into photopolymerization solution.
1mm is thick, the poly--4-methyl-1-pentene film of 20cm * 20cm size, carry out same processing according to embodiment 2, apply above-mentioned photopolymerization solution then equably, under 50 ° ± 5 ℃, with 10 meters/minute speed,, make the surface of this film have water-absorbent to coated film Continuous irradiation ultraviolet ray.
Test-results is as shown in table 1.
Embodiment 8
The polymethylmethacrylate thin plate of thickness 2mm, wide 10cm, long 10cm after the processing of corona discharge machine, applies equably with the photopolymerization solution among the embodiment 7, shines ultraviolet ray in 2 minutes then, makes it surface modification.
Test-results is as shown in table 1.
Embodiment 9
2mm is thick, the polycarbonate thin plate of 10cm * 10cm size, makes the surface of thin plate have water-absorbent according to similarly to Example 8 method.
Described in test-results such as the table 1.
Embodiment 10
Thick 50 microns polyprene film carries out modification according to method similarly to Example 5 and handles.
Test-results is as shown in table 1.
3mm is thick, the polystyrene thin plate of 10cm * 10cm size, carries out 5 minutes the processing of giving with sulphuric acid soln, applies the photopolymerization solution among the embodiment 2 then in the above, utilizes ultraviolet ray to make this polystyrene thin sheet surface modification.
Test-results is shown in Table 1.
Confirm through test, the Dropless high polymer for preparing by embodiment 1-11, its hydrophobic polymer compound chemically combines with hydrophilic monomer or macromolecular compound, and while possess hydrophilic property and hydrophobicity are owing to having carried out crosslinked thereby being not dissolved in water.
Comparative example 1C
Except not carrying out the Corona discharge Treatment, make the surface modification of polyethylene film according to mode similarly to Example 2.
Test-results is shown in Table 1.
Comparative example 2
Except not adding the linking agent, make the surface modification of polyethylene film according to mode similarly to Example 5.
Test-results is shown in Table 1.
Table 1C
The variation of the contact angle of the various films in embodiment and the comparative example and for the weather resistance of water droplet
Can clearly be seen that by the result shown in the table 1 in embodiment 1-11, the contact angle after the processing is 20 ℃-0 ℃, therefore, does not produce water droplet on the surface of film.In addition, weather resistance is also very good.
In contrast, in comparative example 1-2, the contact angle after the processing is before substantially the same with processing, has produced water droplet.In addition, weather resistance extreme difference.
Claims (6)
1, the manufacture method of macromolecule membrane, comprise: macromolecule membrane is carried out surface treatment, water-soluble monomer or water-soluble polymer and linking agent are coated on the surface treated macromolecule membrane with the resulting solution of dissolution with solvents, then to its irradiation ultraviolet radiation.
2, the described manufacture method of claim 1 is characterized in that, macromolecule membrane is to be selected from a kind of in following:
Polyethylene, polyvinyl chloride, polypropylene, polystyrene, polymeric amide-6, polycarbonate, polyprene, polyethylene terephthalate, poly--4-methyl-1-pentene, polymethylmethacrylate.
3, the described method of claim 1 is characterized in that, surface treatment is with a kind of processing that is selected from corona discharge, acid treatment, the gas phase treatment.
4, the described manufacture method of claim 1 is characterized in that, water-soluble monomer is to be selected from a kind of in following:
Vinylformic acid, methacrylic acid, N-vinyl pyrrolidone, acrylamide, Methacrylamide, 2-hydroxyethyl meth acrylate.
5, the described manufacture method of claim 1 is characterized in that, water-soluble polymer is to be selected from a kind of in following:
Polyacrylic acid, poly-N-vinyl pyrrolidone and polyacrylamide.
6, the described manufacture method of claim 1 is characterized in that, linking agent is one or two or more kinds the mixture that is selected from following:
Trimethylolpropane trimethacrylate, Viscoat 295, and three vinylformic acid Ji Wusi (alcohol) esters.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR15982/1988 | 1988-12-01 | ||
| KR1019880015982A KR910005235B1 (en) | 1988-12-01 | 1988-12-01 | Polymer materials with permeability and process for preparation thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1043143A true CN1043143A (en) | 1990-06-20 |
Family
ID=19279814
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN89104723A Pending CN1043143A (en) | 1988-12-01 | 1989-07-15 | The manufacture method of Dropless high polymer |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPH0653821B2 (en) |
| KR (1) | KR910005235B1 (en) |
| CN (1) | CN1043143A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1070547C (en) * | 1996-03-29 | 2001-09-05 | 东丽株式会社 | High-hygroscopicity polyamide fibre, its mfg. method and use |
| CN102585116A (en) * | 2011-12-20 | 2012-07-18 | 浙江鸿盛原汽车用品有限公司 | High-hydroscopicity polyvinyl chloride (PVC) material and preparation method |
| CN102731908A (en) * | 2012-06-27 | 2012-10-17 | 新乡市中科科技有限公司 | Method for continuous hydrophilic modification of polypropylene microporous membrane |
| CN105418955A (en) * | 2015-12-01 | 2016-03-23 | 赵亚平 | Polyvinyl chloride surface modifying method, modifying agent and preparation method thereof |
| CN107983175A (en) * | 2017-12-01 | 2018-05-04 | 天津大学 | Use the high throughput aromatic polyamides reverse osmosis membrane and preparation method of additive |
| CN111925552A (en) * | 2020-08-04 | 2020-11-13 | 佛山金万达科技股份有限公司 | Surface treatment of thermoplastic resin film and resulting product |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE1006883A3 (en) * | 1993-03-05 | 1995-01-17 | Solvay | Surface protection method for items made of thermoplastic material with asurface treatment |
| CN1082518C (en) * | 1998-07-13 | 2002-04-10 | 中国石油天然气总公司石油勘探开发科学研究院 | Method of treatment of fine polyacrylamide powder |
| FR2944982B1 (en) * | 2009-04-30 | 2011-10-14 | Commissariat Energie Atomique | PROCESS FOR PREPARING A METALLIZED SUBSTRATE, ANDTHE SUBSTRATE AND USES THEREOF |
| CN112899215A (en) * | 2017-11-30 | 2021-06-04 | 山西加乐医疗科技有限责任公司 | Cell scaffold and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0640587B2 (en) * | 1987-03-13 | 1994-05-25 | 株式会社東芝 | Semiconductor memory device |
-
1988
- 1988-12-01 KR KR1019880015982A patent/KR910005235B1/en not_active IP Right Cessation
-
1989
- 1989-06-21 JP JP1159398A patent/JPH0653821B2/en not_active Expired - Fee Related
- 1989-07-15 CN CN89104723A patent/CN1043143A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1070547C (en) * | 1996-03-29 | 2001-09-05 | 东丽株式会社 | High-hygroscopicity polyamide fibre, its mfg. method and use |
| CN102585116A (en) * | 2011-12-20 | 2012-07-18 | 浙江鸿盛原汽车用品有限公司 | High-hydroscopicity polyvinyl chloride (PVC) material and preparation method |
| CN102585116B (en) * | 2011-12-20 | 2013-11-27 | 浙江鸿盛原汽车用品有限公司 | High-hydroscopicity polyvinyl chloride (PVC) material and preparation method |
| CN102731908A (en) * | 2012-06-27 | 2012-10-17 | 新乡市中科科技有限公司 | Method for continuous hydrophilic modification of polypropylene microporous membrane |
| CN105418955A (en) * | 2015-12-01 | 2016-03-23 | 赵亚平 | Polyvinyl chloride surface modifying method, modifying agent and preparation method thereof |
| CN107983175A (en) * | 2017-12-01 | 2018-05-04 | 天津大学 | Use the high throughput aromatic polyamides reverse osmosis membrane and preparation method of additive |
| CN107983175B (en) * | 2017-12-01 | 2021-06-29 | 天津大学 | High flux aromatic polyamide reverse osmosis membrane using additives and method of making |
| CN111925552A (en) * | 2020-08-04 | 2020-11-13 | 佛山金万达科技股份有限公司 | Surface treatment of thermoplastic resin film and resulting product |
| CN111925552B (en) * | 2020-08-04 | 2022-11-22 | 佛山金万达科技股份有限公司 | Surface treatment of thermoplastic resin film and resulting product |
Also Published As
| Publication number | Publication date |
|---|---|
| KR910005235B1 (en) | 1991-07-24 |
| KR900009818A (en) | 1990-07-05 |
| JPH02173127A (en) | 1990-07-04 |
| JPH0653821B2 (en) | 1994-07-20 |
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