Polymeric composition

专利摘要:
This invention relates to a sheet-like structure of polyvinyl chloride or a copolymer of vinyl chloride, which is capable of absorbing water vapor and transmitting water vapor, with a uniformly incorporated additive composed of polymeric particles of at least one swellable, modified polymer. The invention also relates to a process for manufacturing the sheet-like structure.
公开号:SU710521A3
申请号:SU772557001
申请日:1977-12-21
公开日:1980-01-15
发明作者:Буш Вальтер；Хольст Арно；Фишер Вильхельм
申请人:Хехст Аг (Фирма)；
IPC主号:

专利说明:

(54) POLYMERIC COMPOSITION where the hydroxyl group, acylamino or esterified carbamino group and hydrogen or carboxyl group. Chemically crosslinked or otherwise pu-. those modified, swelling starch ethers are obtained in such a way that, for example, as a modification, crosslinking is carried out with a crosslinking agent having the following functional groups with respect to hydroxyl groups: НRI i / pu / Igmolvolume, i-n-dN- Bi-H: / dH3. NN J iL gasoline groups X х1 „/ Hat-dltf“ Br о ЯИ1-к- j; asontmi / Hota il-K "(1-0- (ini- (iHsa.uyiia fft // re cua30f Iffofa arugtu or phosphoroxychloride). Another way is that the modification is carried out monofunctionally reactive under the conditions mentioned with respect to i hydroxyl groups of chloma or starch esters with a compound of the general formula: - KI with R - hydrogen or methyl, Kg - hydrogen, RS methyl, CH20H, N-methylene acyl amide group with 1-3 C-atoms esterified with N-methylene carbamide- or N- carboxymethylene carbamide group with 2-7 C-atoms, sludge R and Rj denote methyl or and thus K. and Rg - H or R. denotes hydrogen and R is methyl or R. and Ry is methyl. Water-insoluble highly polymerized carboxymethyl or carboxyethyl cellulose with a significant content of free carboxyl groups is obtained by heating water-soluble acidic compounds up to 8.0-177 C. Cross-linked polymers are produced by pulp grafting side chains of such polymer residues that are selected from ionic and non-ionic polymer residues. Polyacrylic acid, sodium polyacrylate, polymethacrylic acid, potassium polymethacrylate, polyvinyl alcohol sulfate, polyphosphoric acid, polyvinylamine, poly (4-vinylpyridine) are suitable for this purpose. hydrolyzed polyacrylonitrile, polymethyl methacrylate, polyvinyl acetate, polystyrene or polybutadiene. Granular Water-insoluble alkali metal carboxylate salts of starch-acrylonitrile grafted copolymers are obtained by omyling grafted starch-acrylonitrile graft copolymers with a base in an aqueous-alkaline medium. The modified cellulosic material with improved retention of both water and physiological liquids obtained by grafting olefinically unsaturated monomer capable of being polymerized with functional groups capable of being hydrolyzed or a monomer having a carboxyl functional group on the fibrous cellulosic material and a hydrolyzing treatment with alkali grafted product. At the same time, the product is first converted to a state of maximum swelling, then acidified to a pH value at which it has a minimum swelling condition, immediately thereafter under conditions that do not provide swelling, the product is converted to salt and dried immediately after that. The material according to the invention has a good ability to absorb water vapor and vapor permeability. But moreover, the material is also capable of releasing absorbed water vapor under other conditions, for example, when it is located in a different climate. These properties of the material are based on the described said effect of the addition of a part of at least one swelling modified polymer; in addition, they also depend on the thickness of the film or the applied layer, it is advisable to produce films or a layer about 0.05-0.5 mm thick. The material according to the invention with the indicated properties is suitable, for example, in the form of self-supporting films or in the form of a applied layer on the base, especially as a leather substitute (synthetic leather) for the top of the shoe, as buffer linings and upholstery materials (artificial leather and upholstery ) or as an awning material, for example as a material for tents. The description describes the following characteristics of the material and the modified swelling polymers used in it. The ability to retain the water of a swelling modified polymer (wt.%), Measured in relation to the 2000-fold acceleration of gravity, based on its average solvent amount, is determined by immersing the sample in water. The water insoluble portion is defined in a swelling-modified polymer. The degree of substitution, the number of substituted hydroxyl groups of the anhydrous-D-glucose structural unit, varies from 0.0 to 3.0, Absorption ability to swell. a modified polymer for a 1% NaCg solution (weight,%) based on its total weight; absorption capacity is determined by absorbing a 1% solution of NaCl with the sample to saturation. Water absorption is determined by placing the sample in water. Vapor permeability. Inside the device maintain a temperature of 32C; above the specimen - normal conditions (if nothing else is indicated); 20C, B5% .- on the relative air humidity, which is kept constant in the whole device with the help of a rotating fan. The free and breathable surface is 10 cm. Inside the device, using a magnetic stirrer, water is moved at 3-2s, above the atmosphere there is a vapor above the water vapor. The determination of vapor permeability is carried out by determining the reduction in the weight of the vessel with the test sample. Vapor permeability is indicated in mg / cm most often for 1, but also for 8 or 24 hours. Vapor permeability, determined by the gravimetric method. A cup with an absorption agent, closed from the sample using wax, is placed in a humid chamber. The amount of water vapor that penetrates the sample is measured by the change in weight of the cup, this weight gain being linearly dependent on time. Vapor permeability according to this method is the amount of water vapor (g) that passes in 24 hours under constant conditions (temperature, humidity drop through 1 m sample surface. The absorption of water vapor (determined simultaneously with the measurement of vapor permeability). The determination is made by measuring the added weight of the sample. Bending strength The duration of the bending resistance of the lung, the skin, and their coating layers is measured. The skin sample is folded and, in this state, both ends are tensioned in a measuring instrument. One terminal is fastened firmly, and the other moves back and forth, with the result that the fold along the sample changes and changes. Samples are periodically tested to determine if changes have occurred. The experiment can be carried out with a dry, air-conditioned or with a moistened sample. Dry experience serves to test the skin and its tanning. The wet experience serves to evaluate only the dressing. Breaking strength. The tensile strength measurement is performed in a burst experiment. The ultimate tensile strength ffg is the ratio of the measured maximum force (kg) to the initial sample cross-section (cm). Example. Three different swelling modified polymers are examined for several days in a cycle of reversible moisture absorption. A certain amount of polymer is first kept for at least 24 hours in a normal climate (temperature 23 ° С, 50% relative humidity) and weighed. In a rhythm that repeats all the time, the experiment is then carried out, like L-san, below: the polymer sample is 8.0 hours in a humid climate (temperature 80 ° C, 100% relative humidity), then it is weighed, then the sample is within 16.0 h again in a normal climate (23 ° C, 50% relative humidity), then it is weighed again. The obtained measurement value is transferred to the coordinate system (see Fig. 1), on the ordinate from. A weight gain (wt.%) Is added, and the abscissa is the reaction time (h). A continuous line is denoted in FIG. 1, a cycle of reversible moisture absorption of a mixture of bisarylamidoacetic acid crosslinked quaternary ammonium cellulose and cellulose with a water retention capacity of 1.160, a water-insoluble part (98 and absorption capacity of 950, a dashed line indicate a moisture-insoluble part (98 and absorption capacity of 950, a dashed line is water-insoluble part (98 and absorption capacity 950, a dashed line) respectively, of carboxy-methyl starch and carboxymethylcellulose hydrated with bisarylamidoacetic acid and carboxymethylcellulose hydrate with an ability to retain water 11.250, water-insoluble part 85.1 and bsorbtsionnoy ability 1,920 and dots indicate vlagotsikl carboxymethylcellulose, crosslinked via bisakriloamidouksusnoy acid, with the ability to hold water and water-insoluble part of 3,270 97 From comparing individual vlagotsiklov seen that the moisture absorption corresponds cnoco6HbiNm
swell, modified polymers, under certain conditions, can again be highlighted. This property is of great importance in the case, for example, of using these polymers as; material for shoes in the form of films or other types of substrates, since the shoes are worn for a certain time, during which moisture from the foot penetrates into its material, during the period free from wear (for example, at night), the skin material must release this moisture back into the atmosphere .
Examples 12–5. The absorption capacity or absorption value of water vapor was determined for a 0.5 mm thick film made of gray or brown PVC powder with a different amount of abhumable modified polymer (see Table 1). Absorptive capacity was determined by placing the film in water; water vapor absorption was determined at 100% relative air humidity, flexural strength of the modified Hglen in examples 2-4 is good (up to 120,000 bends without cracks), and in Example 5 - bad (more than 500 bends give cracks). The tensile strength decreases in the case of the films of example 2-4 by approximately I5% j in the case of example 5, the films obtained are more durable.
Table
Gray Karbv Bisacryloxy-amidouacmethyl acid volcanic acid is small (cross-linking)
10 20
The Same The Same The Same 4Korich nevy - - 5Grey Carb-Vinyl Oxysulfonmethyl-amide cel (without 10 0.42 17,040. VINE OF MULTI) 6Grey nevy - Examples 6-23. Determined ab-modified polymer (see table.
sorption capacity or absorption-2). The absorptive capacity of the back water vapor of films with a thickness of jj was determined by placing the films in water,
0.3 mm obtained from PVC with the absorption of water vapor determined
personal types capable of swelling in different climatic conditions.
2.700 92.2 1.600 5.0 2.700 92.2 1.600 4.8 7.8 17.7 2.700 92.2 1.600 6.5 9.2 23.2 52.4 1.230 О О
H
but
1L
g
N
hVJ3 rN
40
ID
about of
1L
00
VO
about
one
1L fN
g
"3VO
00 (N
(P
V

About N
P
Chew CN
Vd n
fN fN
(
l
I
N
Tl
In examples L-14, films from PVC plastisol, in Examples 16-19, from brown PVC powder, in Examples 20-23, from brown PVC powder with the addition of 3 wt.% Pore-forming agent.
Examples 24-28. Determine Absorption Capacity, Resistance
PVC - plastisol
24 25 26
10 20 30
27
40
- powder
28
4.7
ten
ABOUT
Carboxymethyl starch is used as a swellable mod1 fitOrn of the polymer, the modifier is everywhere; b; as as;; cyclic acid (crosslinking); water absorption capacity is 2.700; water-insoluble part is 92.2; i.SOO absorption component.
Examples 25-31, Determined. 5. Is the value of vapor permeability to partially the value of the absorption of water n & d of films of thickness OL mm (examples 29-30 or 0-, 3 mm (example 31)) obtained from brown PVC powder. the addition of varying amounts of the swelling-modified modified polymer and compared with the same skin films (see Table 4).
Table 4
stretching and bending resistance of films with a thickness of 0.3 MMf obtained from PVCpl-astnzol (Examples 24-27) or gray PVC powder (Example 28) and with the addition of various amounts of swelling-modified polymer and compared with films, without such additives ( see tab. 3).
Table 3
150000 (good) .105000 (cracks)
120000 (TREDINED)
110000 (cracks)
150000 (good)
105,000 (cracks)
3.8
i 50000 (good)
Continuation of table 4
wt.% i
3;
15
Carboxymethylcellulose, baxacrylamidoacetic acid modifier (crosslinking), substitution degree 1.02, water retention capacity 542, water-insoluble part - 83.8, absorption capacity 1,130 are used as swelling modifiable psliera. For example, water vapor absorption and vapor permeability of films prepared from PVC plastic were determined as a function of film thickness and the amount of carboxymethylcellulose crosslinked with bisacrylamidoacetic acid modified with a polymer with a degree of substitution of 1.02 and water retention of 542 , a water-insoluble part of 83.8 and an absorption capacity of 1.130 when the penetration through a 125 μm sieve. In the coordinate system (see Fig. 2), on the ordinate, the values of water vapor absorption are placed and, on the abscissa, the amount of swelling modified polymer in the film. The absorption of water vapor increases with both the increase in the additive and the increase in the layer thickness. However (see Fig. 3), vapor permeability, although increasing with an increase in the additive, decreases with an increase in the thickness of the layer. If both. measurements (see Fig. 4) can be compared graphically with each other, it can be seen that between the parameters of the layer thickness and the amount of swelling modified polymer it is possible to establish a correlation, which in some cases can be calculated in certain interV as swelling modified polymers used carboxymethylcellulose, bisacrylamidacetic acid modifier (crosslinking), degree of substitution 1.02, ability to retain water 542, absorption capacity 1.130.

Temperature in degrees Celsius, relative humidity in percent. halls. Thus, it becomes clear that it makes no sense to increase the film thickness significantly more than 0.5 mm, just as the amount of swelling modified polymer is advisable to be maintained in the range of about 10-30 wt.% So that the mechanical properties of the film do not change too much. Examples 33-40. The water vapor absorption and vapor permeability (see Table 5) of a 0.2 mm film made of PVC plastisol with the same amount of a swelling modified polymer under different climatic conditions were determined (examples 33-36). In examples 37-40, the amount of additives was varied and, in addition, although chemically comparable polymers were used, when they were obtained, the pH value of the liquid precipitating medium (cross-linked carboxymethylcellulose is obtained in an alkaline medium. Immediately after this, the reaction medium is mixed with acetic acid) was not set as in Example 33-36 to 6, but was set to 8. These crosslinked carboxymethylcellulose particles (Examples 3740) are significantly better than mechanical methods. They are introduced into the molding compound. Table 3 Comparative Examples 1-10. The value of water vapor absorption and vapor permeability of a 0.2 mm thick film obtained from PVC-plastisol with various additives from unmodified carbohydrates or carbohydrate derivatives were determined.
Examples 41-44 and comparative examples 11-13.
Determined the value of the absorption of water vapor and D94YH vapor and the value of vapor permeable MOCTII films with a thickness of 0.2 mm, noJjy of PVC-plastisol with the addition. modified able to swell polymer on samples of different lengths (see tab. 7), examples 41-44.
Table 7
Cellulose powder
40
Continuation of table 7
45
50
 20 wt.% carboxymethyl cellulose modifier — bisacrylamidoacetic acid (crosslinking), degree, substitutions 1.02, water retention capacity 542, water-insoluble part 83.8, absorption capacity 1.130. Aniline leather for shoe upper. Unmodified polyurethane shoe upper material. Leather for the top of the shoe with a coating. (see Table 6) to convincingly prove that the results obtained for the films according to the invention do not indicate the presence of only the transport effect of the introduced particles from the modified swelling polymer, T-a b l and c 6
It turned out that, first of all, vapor permeability, as well as absorption of water vapor (with measurement of excretion) with a measurement time not only absolutely but also for the same basic time (1 hour increases relatively. For comparison, the values of water vapor absorption and vapor permeability of commercial materials comparative examples 11-13.
Examples 45, 46 and comparative examples 14-22.
KSch dispersion micron
ten
Also
20 l Unmodified cellulose dispersion
450 microns (92%)
10 20 20
Also
- Unmodified cellulose dispersion
32 microns (96%)
20 20
Also
Non-dietary corn starch dispersion Substitution ratio .1.02, modifier (cross-linking), ability to retain water, absorption capacity 1.130. p p and m p s 47-55. Determined water vapor absorption and vapor permeability of 0.2 mm thick films obtained from PVC-plastisol with the addition of swelling-modified modified polymer of various types
Bbina is determined by another method of vapor permeability of 0.2 mm thick films obtained from PVC-plastisol without additives (Example 14), with additives according to the invention (Examples 45 and 46) and with additives that are not the subject of the invention (Examples 15-22). The values determined using this method also show that the increased vapor permeability of the films according to the invention cannot be based on only one transport effect of the introduced particles (see Table 8),
Table. eight
15.6
0.65
23
85
85
23
0.73
17.4
1.84
44.2
23
85
0.62
23 23 32
85 85 85 0.54 1.09
0.64
23 32
85 85 1.09 bisacrylamidoacetic acid p, water-insoluble part 83.8, 542 6 (1 (see Table 9). Comparison of these results, for example, with the results of Table 6 (additions of particles of unmodified carbohydrates) also show this increase.
CMC Epichlorohydrin
(stitching) 15
Poly Acrylamide Stitched15
Acri-Tetraallyl-oxetane VA (crosslinking) acid 15
Phosphate
celled- -
Vines 10
CMC High esterified Formula of the Invention Polymer composition containing polyvinyl chloride and additive, in order to increase vapor permeability and vapor absorption of films and coatings obtained from the composition, it contains modified starch ether or cellulose as an additive
Table
0.75 4.400 73.8 1.500 11.73 1.47 13.24
117.000 50.0 3.500 23.18 2.88 20 .300 33.4 1.150 4.02 0.50 1.83
4.650 86.0 1.320 20.092.52 in the following ratio of components, wt.%: Additive 10-30, polyvinyl chloride the rest
Sources of information taken into account in the examination
1. US patent number 3644259, class. C 08 f 29/18, 1972.
2. Japan patent number 20425/73, cl. from 08 f 47/10 (prototype). ,,, ta 30 fo,, ttpfluitffmeo od its i rovaino a polyier vk, /, iO 20 30 to ffajrweeifto modi1i1a (11gr1 polymer, vi, /. Phage. 3

/
X
/
e / taf, mm
Fi.I

权利要求:
Claims (1)
[1]
SUMMARY OF THE INVENTION A polymer composition containing polyvinyl chloride and an additive is related to the fact that, in order to increase the vapor permeability and vapor absorption of the films and coatings obtained from the composition, it contains a modified starch or cellulose ether as an additive in the following the ratio of components, wt.%: additive 10-30, polyvil50 nyl chloride the rest

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同族专利:

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公开号 | 公开日

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ZA777626B|1979-07-25|

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HU175612B|1980-09-28|

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LU76471A1|1978-07-10|

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NL7714267A|1978-06-27|

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FR2375286A1|1978-07-21|

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CA1099060A|1981-04-14|

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PT67438B|1979-05-23|

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CS209498B2|1981-12-31|

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DE2756484C3|1980-09-11|

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BE862143A|1978-06-21|

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FR2375286B1|1983-03-11|

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PL203250A1|1978-09-11|

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法律状态:

优先权:

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申请号 | 申请日 | 专利标题

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LU76471A|LU76471A1|1976-12-24|1976-12-24|

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