CN1060489C - Dropless high polymers and its preparation - Google Patents
Dropless high polymers and its preparation Download PDFInfo
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- CN1060489C CN1060489C CN 89102546 CN89102546A CN1060489C CN 1060489 C CN1060489 C CN 1060489C CN 89102546 CN89102546 CN 89102546 CN 89102546 A CN89102546 A CN 89102546A CN 1060489 C CN1060489 C CN 1060489C
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Abstract
The present invention relates to a dripless high molecular material and a preparation method thereof. A water soluble monomer or a water soluble high molecule and a crosslinking agent are dissolved together in a solvent to be prepared into a solution; the obtained solution is coated on a high molecular film bearing surface treatment and then is irradiated by ultraviolet rays; thereby, the dripless high molecular material of the present invention is prepared.
Description
The invention relates to the macromolecular material and the manufacture method thereof of no condensing water droplet, more particularly, be about water-soluble monomer or water-soluble polymer are dissolved in the macromolecular material and the manufacture method thereof of the no condensing water droplet that resulting solution is coated on the surface treated macromolecule membrane in the solvent, make with uviolizing with linking agent.
Macromolecule membrane is owing to having the favorable mechanical performance, gentle being widely used than property, nontoxicity and optical property etc.
But there are some problems in its surface properties of macromolecule membrane in the past.For example, with the simple greenhouse that macromolecule membrane is in the past built, the water vapour in its room air can be agglomerated on the surface of film or polymer thin plate, has reduced indoor transparency, thereby has hindered the g and D of plant.Also have, on the capsule that the agglomerative water droplet falls on the leaf of plant, germinateing or on the leaf of flower, the result makes these plants withered.
Use macromolecule membrane to make the occasion of packaging material for food, impelling spoilage owing to producing water droplet sometimes.
In the past, the method that adopted in order to address these problems has: the method for coating special surface promoting agent, in high molecular film material mixing no water droplet condensing agent method, utilize radioactive rays and Low Temperature Plasma Treating to make the method for water-soluble polymer graft polymerization, carry out the method for graft polymerization etc. by UV treatment.
In these methods, if adopt the method for coating special surface promoting agent, then owing to the layer thickness that contains no water droplet condensing agent is thinner, thereby water-retaining capacity is little, poor durability.In addition,, so, produce emulsifying effect owing to this tensio-active agent and attached to the water droplet on the film surface in use, make no water droplet condensing agent be easy to flow out if the special surface promoting agent that uses is the hydrophilic surfactant active.Therefore, the method for coating special surface promoting agent, though use the initial stage effect fine, persistence is very poor, this is its shortcoming.
In addition, if adopt the method for mixing no water droplet condensing agent in macromolecule membrane, because the resin that uses is very poor with the consistency of no water droplet condensing agent, no water droplet condensing agent is gone on the surface of film, therefore on film, produce opaque part, the uneven phenomenon of solar ray transmission occurred.If the no water droplet condensing agent that it is good that this phenomenon is selected consistency for use is avoidable,, because the good no water droplet condensing agent of consistency is hydrophilic, if on the surface of film, have no water droplet condensing agent, it will be separated out by the water droplet dissolving, thereby reduced no water droplet, under this occasion, also can produce opaque part.That is to say, when using this hybrid type thin film, can produce opaque section to a certain degree inevitably.
Utilize radioactive rays and Low Temperature Plasma Treating to make the method for water-soluble polymer and film graft polymerization, its advantage is an obvious processing effect, and treatment effect is rich in diversity, but the initial stage cost of equipment of this method is high, manufacturability and productivity are lower, owing to there is such shortcoming thereby is difficult to practicability.
In contrast, utilize ultraviolet to make the method for macromolecule membrane graft polymerization more simple and easy to do, therefore be used to improve character such as printability and tackiness more effectively than the above-mentioned method of radioactive rays and low temperature plasma polymerization of utilizing.But iff relying on this graft polymerization, the macromolecule membrane as being fit to agricultural film etc. still lacks the weather resistance for water droplet and other surrounding environment, and this is its maximum shortcoming.
The present invention adopts and to utilize light to make the water-soluble monomer graft polymerization, carry out crosslinked method simultaneously under the condition that light trigger exists, the polymer substance of the noncondensing water droplets such as polyolefin film with fabulous no water droplet is provided, this method is carried out continuously, has facility investment and low holds concurrently, can adopt and be easy to manufacture method and characteristics such as carry out.In addition, the coating thickness of the polymer substance of no condensing water droplet of the present invention with formation is lower than almost characteristics such as increase not of 1 μ, overall weight.
That is to say, the macromolecular material of no condensing water droplet of the present invention, it is characterized in that, from polyethylene, polyvinyl chloride, polypropylene, polystyrene, polymeric amide-6, polycarbonate, polyethylene terephthalate, poly--4-methyl-1-amylene, polymethylmethacrylate, select at least a high molecular film material in the polyprene, use corona discharge, acid treatment, at least a method in the gas phase treatment is carried out surface treatment to it, from vinylformic acid, methacrylic acid, the vinylchlorid pyrrolidone, acrylamide, Methacrylamide, select at least a compound in the water-soluble monomers such as 2-hydroxyethyl meth acrylate or from polyacrylic acid, the polyvinyl chloride pyrrolidone, select at least a compound in the water-soluble polymers such as polyacrylamide, with its be selected from the allyl methyl acrylate, ethylene glycol dimethacrylate, N, N '-methylene radical-bisacrylamide at least-kind of a crosslinker compound dissolves together, gained solution is coated on the above-mentioned surface treated high molecular film material, the no condensing water droplet polymer substance that its irradiation is obtained with ultraviolet ray.
The manufacture method of the macromolecular material of no condensing water droplet of the present invention, it is characterized in that, from polyethylene, polyvinyl chloride, polypropylene, polystyrene, polymeric amide-6, polycarbonate, polyethylene terephthalate, poly--4-methyl-1 one amylene, polymethylmethacrylate, select at least a high molecular film material in the polyprene, use corona discharge, acid treatment, at least a method in the gas phase treatment is carried out surface treatment to it, from vinylformic acid, methacrylic acid, the vinylchlorid pyrrole is alkane ketone slightly, acrylamide, Methacrylamide, select at least a compound in the water-soluble monomers such as 2-hydroxyethyl meth acrylate or from polyacrylic acid, the polyvinyl chloride pyrrolidone, select at least a compound in the water-soluble polymers such as polyacrylamide, with this compound be selected from the allyl methyl acrylate, ethylene glycol dimethacrylate, N, at least a crosslinker compound of N '-methylene radical-bisacrylamide dissolves together, gained solution is coated on the above-mentioned surface treated high molecular film material, then the manufacture method that its irradiation is constituted with ultraviolet ray.
Operable in the present invention macromolecule membrane, be those in a single day be subjected to illumination just can produce the atomic group that can cause graft polymerization, ion etc. and on high molecular main chain or side chain, can generate can the initiated polymerization reactive site macromolecular material.More particularly, can use the macromolecule membrane of making by materials such as polyethylene, polyvinyl chloride, polypropylene, polystyrene, polymeric amide-6, polycarbonate, polyethylene terephthalate, poly--4-methyl-1-amylene, polymethylmethacrylate, polyprenes.
In the above-mentioned macromolecular material, can produce on side chain that the polymer of reactive site is adducible to be had: polystyrene, polypropylene, polyethylene, poly--4-methyl-1-amylene, polymethylmethacrylate, polymeric amide-6 etc.; The polymer that can produce reactive site on main chain can be enumerated polyprene.
Operable in the present invention water-soluble monomer can list: vinylformic acid, methacrylic acid, acrylamide, 2-methylol methacrylic ester, 2-hydroxyethyl meth acrylate, vinylchlorid pyrrolidone etc.
In addition, water-soluble polymer can use single polymers that is made of above-mentioned water-soluble monomer and the multipolymer that is made of the monomer more than two kinds, promptly can use polyacrylic acid, polyvinyl chloride pyrrolidone, polyacrylamide etc.
In the present invention, carry out graft polymerization,, make it crosslinked bonding with linking agent in order further to improve persistence through the noncondensing water droplet of macromolecule membrane of such graft polymerization for the character of giving the noncondensing water droplet of macromolecule membrane.
At this moment employed linking agent, adducible have: N, N '-methylene radical-bisacrylamide, allyl methyl acrylate, ethylene glycol dimethacrylate and their derivative.
In the present invention,, can use methyl alcohol, ethanol, acetone, ethyl methyl ketone and water, perhaps use above-mentioned suitable mixed solution more than two kinds as making dissolved solvents such as water-soluble monomer, water-soluble polymer, light trigger, linking agent.
In the present invention, for the photopolymerization solution that water-soluble monomer, water-soluble polymer, linking agent, light trigger etc. are mixed is coated on the macromolecule membrane equably, also carry out easily simultaneously, macromolecule membrane is imposed surface treatments such as Corona discharge Treatment, gas phase treatment, liquid phase chemical processing for the graft polymerization that makes macromolecule membrane and water-soluble monomer or water-soluble polymers.
Corona discharge Treatment can be undertaken by any mode in spark gap formula or the electron tubes type.Liquid phase chemical is handled any treatment process that can adopt sulphuric acid soln, bichromate solutions, calcium permanganate solution and surface to add in the moisture solution and is carried out.Gas phase treatment can adopt any treatment process in fireworks processing, ozonize, oxygen processing, chlorine processing, sulfur dioxide gas processing, the nitrogen dioxide gas processing to carry out.In addition, can also carry out surface treatment with ultraviolet ray.
In the present invention, utilize ultraviolet ray to make water-soluble monomer or water-soluble polymers graft polymerization.
At this moment the light source of Shi Yonging is to make light trigger decompose, form the light source at atomic group, ion isoreactivity position.Operable light source has: wavelength is Cooper-Hewitt lamp, fluorescent lamp, xenon lamp, metal halide lamp, the Le Shi of section Jupiter (Kern-arc lamp), tengsten lamp, solar ray of 200-700nm etc.
The ideal irradiation time is 0.1 second to 24 hours.
As light trigger, can use benzophenone, phenyl methyl ketone, isopropyl diphenyl base ethanol ether ketone, benzoyl peroxide, N, N '-Diisopropyl azodicarboxylate etc.
In the present invention, the noncondensing water drop test of surface treated macromolecule membrane is carried out by the following method:
Put into water to the 4.5cm height in the beaker of diameter 8cm, high 10cm, water temperature generally remains on 40-45 ℃.Then, surface treated film is placed on the top of beaker, checks the persistence of its noncondensing water droplet, measure its contact angle for each film.
Below enumerate embodiment and illustrate in greater detail the present invention, but, the present invention is not subjected to the qualification of these embodiment.
Embodiment 1
With the high-pressure mercury lamp as light source of 400 W, it is arranged on the film top apart from film 10cm place, 30cm is provided with 5 continuously at interval.
100g vinylformic acid, 42gN-vinyl pyrrolidone, 18g benzophenone and 10g are dissolved in the 410g acetone equably as the ethylene glycol dimethacrylate of linking agent, are modulated into photopolymerization solution.
Adopt corona treatment that the polypropylene film of thick 30 μ, wide 15cm is carried out the surface and give processing, output rating is that 200W, speed are 5 meters/minute, then, apply the thick above-mentioned photopolymerization solution of 5 μ with pickling process, after this, under 50 ± 5 ℃ of temperature with 5 meters/minute speed irradiation ultraviolet radiation, carry out surface improvements.
Test-results is shown in Table 1.
Embodiment 2
100g vinylformic acid, 54g acrylamide and 20g benzophenone, 14g allyl methyl acrylate are mixed in the 490g methyl ethyl ketone equably, are modulated into photopolymerization solution.
The P.V.C film of thick 50 μ, wide 20cm, with nitrogen dioxide gas or chlorine treatment after 15 minutes, wash its surface with water, dry back applies above-mentioned copolymerization solution equably with pickling process on film, under 50 ± 5 ℃ with 5 meters/minute speed Continuous irradiation ultraviolet ray, carry out surface modification.
Test-results is shown in Table 1.
Embodiment 3
With 180g vinylformic acid, 5g polyacrylic acid, 20g phenyl methyl ketone, and 10g ethylene glycol dimethacrylate, 2gN, N '-Diisopropyl azodicarboxylate is mixed into equably makes it dissolving in the 500g ethanol, be modulated into photopolymerization solution.
The polyethylene film of thick 75 μ, wide 20cm gives processing according to method similarly to Example 1 with the corona discharge machine, utilizes coating machine to apply above-mentioned photopolymerization solution in the above equably then.Be placed under 50 ± 5 ℃, under the condition that has nitrogen gas stream to exist with 1.5 meters/minute speed continuously to its irradiation ultraviolet radiation, carry out the surface modification of film.
Experimental result is shown in Table 1.
Embodiment 4
With 42g methacrylic acid, 25gN-vinyl pyrrolidone, 27g polyvinylpyrrolidone, 18g isopropyl diphenyl base ethanol ether ketone and 10gN, N '-methylene radical-bisacrylamide is dissolved in the 600g methyl alcohol, is modulated into photopolymerization solution.
Polymeric amide-6 film of thick 50 μ, wide 20cm after giving processing described in the embodiment 1, applies the thick above-mentioned photopolymerization solution of 5 μ with coating machine.Under 50 ± 5 ℃ with 4 meters/minute speed continuously to its irradiation ultraviolet radiation.
Experimental result is shown in Table 1.
Embodiment 5
130g vinylformic acid, 18g benzophenone, 10g ethylene glycol dimethacrylate are dissolved in the 410g acetone equably, are modulated into photopolymerization solution.
The polyethylene film of thick 25 μ, wide 20cm, through similarly to Example 1 give processing after, apply above-mentioned photopolymerization solution equably with pickling process.Under 50 ± 5 ℃ with 1.5 meters/minute speed continuously to its irradiation ultraviolet radiation.
Result of implementation is shown in Table 1.
Embodiment 6
The pet film of thick 12 μ, wide 20cm, the NaOH aqueous solution with 15% carries out after the surface adds water decomposition and handle, apply the thick photopolymerization solution identical of 5 μ in the above equably with embodiment 1, under 50 ± 5 ℃ with 5 meters/minute speed to its irradiation ultraviolet radiation, carry out surface modification.
Test-results is shown in Table 1.
Embodiment 7
The polystyrene film of thick 3mm, wide 10cm, long 10cm, with sulfuric acid give handle 5 minutes after, identical photopolymerization solution among coating and the embodiment 5 carries out surface modification to its irradiation ultraviolet radiation.
Result of implementation is shown in Table 1.
Embodiment 8
54g methacrylic ester, 130g 2-hydroxyethyl meth acrylate, 20g-benzophenone and 14g allyl methyl acrylate are mixed in the 580g ethanol equably, are modulated into photopolymerization solution.
Poly--4-methyl-1-amylene of thick 1mm, wide 20cm, after giving processing according to embodiment 1 is described with the corona discharge machine, the even above-mentioned photopolymerization solution of coating in the above, under 50 ± 5 ℃ with 4 meters/minute speed continuously to its irradiation ultraviolet radiation, carry out surface modification.
Test-results is shown in Table 1.
Embodiment 9
The polymethyl methacrylate film of thick 2mm, wide 10cm, long 10cm, give processing with the corona discharge machine after, coating photopolymerization solution similarly to Example 8 equably in the above, carries out surface modification at irradiation ultraviolet radiation 5 minutes.
Test-results is shown in Table 1.
Embodiment 10
The polycarbonate film of thick 2mm, wide 10cm, long 10cm carries out surface modification according to method similarly to Example 9.
Test-results is shown in Table 1.
Embodiment 11
The polyprene film of thick 50 μ, wide 20cm carries out surface modification according to method similarly to Example 5.
Experimental result is shown in Table 1.
Verified, the no condensing water droplet polymer substance of making in the foregoing description 1-11, because hydrophobic polymer compound and hydrophilic monomer or macromolecular compound are chemically combined, so while possess hydrophilic property and hydrophobicity, and because therefore being crosslinked be not dissolved in water.
Comparative example 1
Except not carrying out Corona discharge Treatment, according to implement 1 same mode polypropylene film carried out surface modification.
Test-results is listed in the table 1.
Comparative example 2
Except not adding ethylene glycol dimethacrylate, the method light modulated polymeric solution according to similarly to Example 5 utilizes ultraviolet ray to carry out photopolymerization then.
Test-results is shown in Table 1.
Table 1
Surface treated various in embodiment and comparative example
The variation of the contact angle of film reaches the weather resistance to water droplet
| Test subject | Contact angle | Weather resistance to water droplet | Remarks | ||
| Example is not | Sequence number | Before the processing | After the processing | ||
| Embodiment | 1 2 3 4 5 6 7 8 9 10 11 | 91° 93° 107° 87° 107° 90° 90° 93° 64° 80° 84° | 20°-0° 20°-0° 20°-0° 20°-0° 20°-0° 20°-0° 20°-0° 20°-0° 20°-0° 20°-0° 20°-0° | More than three months more than three months more than three months more than three months more than three months more than three months more than three months more than three months more than three months more than three months more than three months | |
| Comparative example | 1 | 107° | -100° | Less than three days | Do not carry out Corona discharge Treatment |
| 2 | 107° | -100° | Less than three days | Do not add linking agent | |
Can be clear that by the result shown in the table 1. implementing in 11-11.Because the contact angle after handling is 20 °-0 °, therefore on the surface of film, do not produce water droplet fully, and weather resistance is also very good.
In contrast, in comparative example 1-2, the contact angle after the processing with handle before contact angle much at one, thereby produce water droplet, and the weather resistance extreme difference.
The manufacture method of no condensing water droplet macromolecule membrane of the present invention, overcome the shortcoming of macromolecule membrane, simultaneously do not reduce its inherent mechanical property, can obtain on the surface of film, not forming fully the no condensing water droplet macromolecule membrane of water droplet in this way.
Claims (1)
1, a kind of macromolecular material that does not have condensing water droplet is characterized in that, described macromolecular material prepares by the following method:
From polyethylene, polyvinyl chloride, polypropylene, polystyrene, polymeric amide-6, polycarbonate, polyethylene terephthalate, poly--4-methyl-1-amylene, polymethylmethacrylate, select at least a high molecular film material in the polyprene, use corona discharge, acid treatment, at least a method in the gas phase treatment is carried out surface treatment to it, from vinylformic acid, methacrylic acid, the vinylchlorid pyrrolidone, acrylamide, Methacrylamide, select at least a compound in 2-hydroxyethyl meth acrylate water-soluble monomer or from polyacrylic acid, the polyvinyl chloride pyrrolidone, select at least a compound in the polyacrylamide water-soluble polymer, with this compound be selected from the allyl methyl acrylate, ethylene glycol dimethacrylate, N, at least a crosslinker compound of N '-methylene radical-bisacrylamide dissolves together, gained solution is coated on the above-mentioned surface treated high molecular film material, with ultraviolet ray it is shone then.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89102546 CN1060489C (en) | 1989-04-26 | 1989-04-26 | Dropless high polymers and its preparation |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89102546 CN1060489C (en) | 1989-04-26 | 1989-04-26 | Dropless high polymers and its preparation |
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| Publication Number | Publication Date |
|---|---|
| CN1046742A CN1046742A (en) | 1990-11-07 |
| CN1060489C true CN1060489C (en) | 2001-01-10 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 89102546 Expired - Fee Related CN1060489C (en) | 1989-04-26 | 1989-04-26 | Dropless high polymers and its preparation |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10325437A1 (en) * | 2003-06-05 | 2004-12-23 | Bayer Materialscience Ag | Polycarbonate molded body with low Staubanziehung |
| CN100344654C (en) * | 2005-07-14 | 2007-10-24 | 中国科学院长春应用化学研究所 | Method for preparing water soluble polymer material |
| CN107955989A (en) * | 2017-07-17 | 2018-04-24 | 福建省晋江市华宇织造有限公司 | Nano bionic waterproof material for the imitative lotus leaf effect in screen cloth field |
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