CN100343288C - Crosslinked polyvinyl acetals - Google Patents
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- CN100343288C CN100343288C CNB2003801101334A CN200380110133A CN100343288C CN 100343288 C CN100343288 C CN 100343288C CN B2003801101334 A CNB2003801101334 A CN B2003801101334A CN 200380110133 A CN200380110133 A CN 200380110133A CN 100343288 C CN100343288 C CN 100343288C
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Abstract
The invention relates to methods for producing crosslinked polyvinyl acetals, according to which a polyvinyl alcohol (A1) containing carboxyl groups is crosslinked by (i) reacting the polymer (A1) with at least one polyaldehyde of formula R<SUP>9</SUP>(CHO)<SUB>n</SUB>, and (ii) at least partly esterifying groups of formula (1) and formula (4a) with each other, said steps being performed in any order. The invention further relates to methods for producing crosslinked polyvinyl acetals, according to which a polyvinyl alcohol (A2) is crosslinked by (i) reacting the polymer (A2) with at least one compound of formula (6), (ii) adding at least one compound of formula (4b), (iii) adding a polyaldehyde of formula (5), and (iv) at least partly esterifying groups of formula (1) and structural units derived from the compound of formula (4b) with each other, the radicals R<SUP>7</SUP>, R<SUP>8</SUP>, R<SUP>9</SUP>, R<SUP>10</SUP>, and R<SUP>11</SUP>, and the index n being defined as indicated in the description. Also disclosed are the crosslinked polyvinyl acetals obtained by means of the inventive method and particularly appropriate areas of application of said polymer.
Description
The present invention relates to cross-linked pioloform, its preparation method with and use, especially for laminated safety glass.
With butyraldehyde-n polyvinyl acetal being carried out modification especially by means of acetalization is a kind of for a long time known and reaction that often utilize.The film of the polyvinyl acetal that in this way obtains, particularly polyvinyl butyral acetal, owing to its higher light resistance and good viscosifying power thereof are used as laminated safety glass, the middle layer in the automotive window (front window and side window) particularly.This laminated glass can provide the security of higher degree, because when being subjected to shock stress, elastic polyvinyl acetal film can absorb mechanical energy, and can make also that wherein issuable glass disintegrating slag is sticking to be stayed on this film.
But, usually do not have sufficient mechanical property based on the laminated safety glass of traditional polyvinyl acetal type, particularly under greater than 150 ℃ higher temperature.The method of ultra high molecular weight polyethylene acetal also is difficult to be resolved even this problem has more by use, because when this situation, especially can (for example form bubble because of its processing problems, the viscosity of polyvinyl acetal is too high or too low under processing temperature, and it is non-constant to add man-hour character) and make the actual feasibility degree that reaches capacity.
For this reason, recommend to use a kind of polyvinyl butyral acetal among European patent application EP 0211818 A1, it is to have under the situation of aldehyde of at least two aldehyde radicals in use, via intermolecular two acetal bondings, and before the acetalation of polyvinyl alcohol or in mutually crosslinked with butyral.But this crosslinked meeting causes generating strong crosslinked very high molecular owing to the greater activity of aldehyde and also is the insoluble polyvinyl butyral acetal of part therefore, and this product---if having---very limitedly be applicable to the laminated safety glass for preparing better quality.Do not consider the words of this point, those neither be sufficiently stable under polymeric thermoplastic processing (for example extruding) condition by the crosslinked polyvinyl butyral acetal of dialdehyde or polyacetals (Polyaldehyde), therefore according to crosslinked positions of factor such as used temperature, the residence time, shearing rates more or less tangible separation phenomenon (molecular weight decomposition) can take place.But these defectives of thermostability aspect have just increased the difficulty that particularly obtains the quality product of repetition, because the reactivity of polymkeric substance changes very sensitivity for producing, and these defectives also can cause the deterioration of polyvinyl acetal mechanical property, particularly under comparatively high temps.
Therefore, in view of prior art, it is a kind of particularly under higher temperature that task of the present invention is to provide, and is preferably greater than the polyvinyl acetal that better mechanical property is arranged under 150 ℃ the temperature.Simultaneously, polyvinyl acetal of the present invention also should can be suitable for preparing film and being particularly suitable for preparing the laminated safety glass that better quality is arranged especially, and also can make material property in the process of processing film forming and laminated safety glass thus, particularly mechanical property has better unchangeability.
Task of the present invention also is, a kind of method that can prepare polyvinyl acetal of the present invention simple, fairly large and inexpensively is provided.
Task more of the present invention is to look forward to the specially suitable application scenario of polyvinyl acetal of the present invention.
Clearly not listing of the task that can derive or find out be had no difficulty by content discussed herein though these tasks and other do not spell out can be solved by a kind of cross-linked pioloform that is made by the preparation method with all technical characteristic described in claim 1 or 5.The rational improvement project of some of the inventive method falls in the protection domain of the dependent claims of quoting claim 1 and/or 5.In addition, the application interested especially use-pattern and use field of also having asked for protection polyvinyl acetal obtained by the method for the present invention and being used for application target.
By following two kinds of methods just can with non-obvious mode obtain crosslinked and particularly at comparatively high temps, be preferably greater than better mechanical property arranged under 150 ℃, it at first is the polyvinyl acetal of higher storage modulus, in first kind of method for preparing cross-linked pioloform, make a kind of in its gross weight, the polymkeric substance (A1) that contains following structural unit is crosslinked
A) the structural unit of 1.0 to 99.9 weight % with formula (1)
R wherein
1Expression hydrogen or methyl,
B) structural unit of the formula of 0 to 99.0 weight % (2)
R wherein
2Expression hydrogen or have the alkyl of 1 to 6 carbon atom,
C) structural unit of the formula of 0 to 70.0 weight % (3)
R wherein
3, R
4, R
5And R
6Be molecular weight separately independently of each other at 1 to 500g/mol group,
D) structural unit of the formula of 0.00001 to 30.0 weight % (4a)
R wherein
7The expression singly-bound has the alkylidene group of 1 to 10 carbon atom or has 6 to 12 carbon atoms and optional substituted arylidene, and R
8Represent hydrogen, COOH, have the alkyl of 1 to 10 carbon atom or have 6 to 12 carbon atoms and optional substituted aryl,
And can carry out following steps in any order,
(i) polymkeric substance (A1) and at least a polyacetals reaction with formula (5),
R
9(CHO)
n (5)
R wherein
9Expression singly-bound or have the group of 1 to 40 carbon atom, and n be more than or equal to 2 integer and
The (ii) group of interesterification formula (1) and formula (4a) at least in part,
In second kind of method for preparing cross-linked pioloform, make a kind ofly in its gross weight, the polymkeric substance (A2) that contains following structural unit is crosslinked,
A) the structural unit of 1.0 to 99.9 weight % with formula (1),
B) the structural unit of 0 to 99.0 weight % with formula (2),
C) the structural unit of 0 to 70.0 weight % with formula (3),
And wherein
(i) polymkeric substance (A2) and at least a compound reaction with formula (6),
R wherein
10And R
11Be hydrogen independently of each other separately, have the alkyl of 1 to 10 carbon atom or have the optional substituted aryl of 6 to 12 carbon atoms,
(ii) add at least a compound with formula (4b),
R wherein
7The expression singly-bound has the alkylidene group of 1 to 10 carbon atom or has 6 to 12 carbon atoms and optional substituted arylidene, and R
8Represent hydrogen, COOH, have the alkyl of 1 to 10 carbon atom or have 6 to 12 carbon atoms and optional substituted aryl,
(iii) add polyacetals with formula (5) and
(iv) interesterification formula (1) and derived from the group of the structural unit of formula (4b) compound at least in part.
Simultaneously, cross-linked pioloform of the present invention also has a series of other advantages.These advantages especially comprise:
The characteristics of=＞polyvinyl acetal of the present invention are its material character, particularly its mechanical property, as its storage modulus better homoeostasis are arranged.This advantage particularly is higher than under 150 ℃ the temperature and also can observes particularly under comparatively high temps.In category of the present invention, do not observe the situation that the cross-linking density described in EP0211818 A1 changes, on the contrary, polyvinyl acetal of the present invention is even under higher temperature, particularly is being higher than under 150 ℃ the temperature, and it also has significantly better cross-linking density unchangeability.
=＞in polymkeric substance of the present invention connects the carboxyl of polymkeric substance or the existence of carboxylic acid ester groups and can make the point of connection that produces via the acetal bonds bridge be subjected to tangible stabilization.In addition, they also can play shock absorption and come the influence that effectively opposing may deleterious acid by this way, for example by the influence of the deleterious acid of the caused possibility of the hydrolysis prods of caking inhibiter.
=＞can make cross-linked pioloform of the present invention on a large scale and inexpensively with easy method.Wherein, can avoid producing those and can cause the polymkeric substance variable color usually, also therefore for being used as (transparent) laminated safety glass, mean the oxidizing reaction of quality impairment and/or the side reaction of other thermal initiation especially by looser crosslinking reaction condition and required for this reason crosslinking time in short-term especially.
=＞can be comparatively fast and condition prepare cross-linked pioloform of the present invention loosely, thereby because polyvinyl acetal has very high molecular weight when beginning, and can select very short to extrude the distance or the forcing machine residence time.
=＞because its distinctive performance, polyvinyl acetal of the present invention is specially adapted to laminated safety glass, and its can be with easy method, on a large scale and inexpensively, particularly make by extrusion molding.Relevant therewith, at first be to have following advantage, be that the polyvinyl acetal of the application of the invention can avoid bubble to generate in the course of processing and the fluctuation of character to greatest extent, and obtain the high laminated safety glass of better optics and mechanical property and repetition rate by this method.
According to first aspect, the present invention relates to a kind of from polymkeric substance (polyvinyl acetal that the A1) obtains, it contains in its gross weight,
A) the structural unit of 1.0 to 99.9 weight % with formula (1)
B) structural unit of the formula of 0 to 99.0 weight % (2)
C) structural unit of the formula of 0 to 70.0 weight % (3)
D) 0.00001 to 30.0 weight %, the structural unit of the formula (4a) of preferred 0.1-30.0 weight %
Wherein each structural unit naturally can be different mutually, and in category of the present invention, the structural unit of formula (3) does not comprise formula (1), (2) and/or structural unit (4a).
Radicals R
1Represent hydrogen or methyl separately independently of each other, be preferably hydrogen.
Radicals R
2Expression hydrogen or have the alkyl of 1 to 6 carbon atom, be preferably alkyl with 1 to 6 carbon atom, be desirably methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, n-pentyl or n-hexyl, be preferably methyl or ethyl, be preferably methyl especially.
Radicals R
3, R
4, R
5And R
6Being molecular weight separately independently of each other at 1 to 500g/mol group, is hydrogen ideally, and optional is aliphatic series or alicyclic group side chain, that have 1 to 16 carbon atom, and its optional one or more carboxylic acid amide groups and/or sulfonic acid group of containing.
Radicals R
7It is singly-bound, have the alkylidene group of 1 to 10 carbon atom or have 6 to 12 carbon atoms and optional substituted arylidene, be desirably hydrogen or methylene radical, ethylidene, positive propylidene, isopropylidene, positive butylidene, sec.-butylidene, uncle's butylidene, positive pentylidene or positive hexylidene, and it optionally have one or more COOH groups as substituting group.
Radicals R
8Expression hydrogen, carboxyl or have the alkyl of 1 to 10 carbon atom or have 6 to 12 carbon atoms and optional substituted aryl, be desirably hydrogen or methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, the tertiary butyl, n-pentyl or n-hexyl, and it optional contains one or more COOH groups as substituting group.Particularly preferred radicals R
8Comprise hydrogen, methyl and-CH
2COOH.
The structural units derived of particularly preferred formula (3) is from alkene straight or branched, that have 2 to 18 carbon atoms, (methyl) acrylamide and/or vinyl sulfonic acid.Wherein useful especially alkene is verified, and especially those have the two keys of terminal C-C and preferably have alkene, the especially ethene of 2 to 6 carbon atoms.In addition, according to the present invention, the structural unit (3) of derived from acrylamides propenyl sulfonic acid (AMPS) also can bring extremely useful effect.
The structural unit of through type (1) and the acetalization of oxoethanoic acid can access the structural unit of particularly preferred formula (4).
According to second aspect, the present invention relates to a kind of polyvinyl acetal that obtains by polymkeric substance (A2), it contains in its gross weight,
A) structural unit of the formula of 1.0 to 99.9 weight % (1),
B) structural unit of the formula of 0 to 99.0 weight % (2),
C) structural unit of the formula of 0 to 70.0 weight % (3).
Wherein each structural unit naturally can be different mutually, and in category of the present invention, the structural unit of formula (3) does not comprise the structural unit of formula (1) and/or (2).
In addition, radicals R
1To R
6As above definition.
For polymkeric substance (A1) and/or composition (A2), preferably have following content:
The sum of the structural unit of formula (2) is preferably 0.1 to 40mol%, more preferably 0.5 to 25.0mol%, in 1.0 to 15.0mol% scope, all in the sum of the structural unit of formula (1) and (2).Wherein, according to first preferred implementation of the present invention, used polymkeric substance (A1) and/or (A2) in the sum of the structural unit of formula (1) and (2) contains the structural unit of 1.0 to 2.0mol% formula (2).According to second preferred implementation of the present invention, used polymkeric substance (A1) and/or (A2) in the sum of the structural unit of formula (1) and (2) contains the structural unit of 3.0 to 7.0mol% formula (2).According to the 3rd preferred implementation of the present invention, used polymkeric substance (A1) and/or (A2) in the sum of the structural unit of formula (1) and/or (2) contains the structural unit of 10.0 to 15.0mol% formula (2).
According to another particularly preferred embodiment of the present invention, polymkeric substance (A1) and/or (A2) contain each in its gross weight,＞50.0 weight %, weight % comparatively reasonably＞60.0, advantageously＞70.0 weight %, especially＞80.0 the structural unit of weight % with formula (1) and/or (2).Use those contain each in its gross weight＞85.0 weight %, comparatively reasonably＞90.0 weight %, advantageously＞95.0 weight %, the polymkeric substance (A1) and/or (A2) of the structural unit of weight % especially＞99.0 with formula (1) and/or formula (2), just can obtain particularly advantageous result.
In category of the present invention, polymkeric substance (A1) and/or (A2) have syndiotaxy, isotaxy and/or an atactic chain structure.In addition, it can also exist with random and form segmented copolymer.
According to the present invention, polymkeric substance (A1) and/or viscosity (A2) are comparatively accessory, both can use the low-molecular-weight high molecular weight polymers (A1) and/or (A2) also can used in principle.In category of the present invention verified polymkeric substance (A1) and/or viscosity (A2) 1 to 70mPas, preferred 2 to 40mPas, (record down and with the aqueous solution form of 4 weight % at 20 ℃ according to H ppler, DIN 53015) are very favourable in preferred especially 3 to 30mPas the scope.
In addition, polymkeric substance (A1) or molecular weight (A2) also have no particular limits, but for the object of the invention still confirms, special preferred polymers (A1) and/or (A2) have the weight-average molecular weight of 20000g/mol at least.Wherein, weight-average molecular weight is comparatively reasonably measured under the situation of using polyethylene oxide-demarcation thing preferably by means of gel permeation chromatography.
Polymkeric substance that will use among the present invention (A1) and/or preparation (A2) can be carried out with a kind of multistep processes simply.In the first step, at suitable solvent, normally water or alcohol is as in methyl alcohol, ethanol, propyl alcohol and/or the butanols, and under the condition of the suitable radical initiator of use the corresponding vinyl ester of radical polymerization.If carry out polyreaction having under the monomeric condition of free redical copolymerization, then can obtain corresponding vinyl ester copolymer.
Then in second step, come saponification vinyl ester (being total to) polymkeric substance by carry out transesterification reaction with methyl alcohol usually, wherein available currently known methods is as on purpose regulating saponification deg by changing catalyst concn, temperature of reaction and/or reaction times.Other detail content can be with reference to general technical literature, Ullmann ' s Encyclopedia of IndustrialChemistry particularly, the 5th edition, CD-Rom Wiley-VCH, 1997, Keyword:Poly (VinylAcetals) and wherein cited reference.
Polyvinyl alcohol from this way obtaining can make polymkeric substance (A1) by reaction and the acetalization with the compound with formula (4b) then,
R wherein
7The expression singly-bound has the alkylidene group of 1 to 10 carbon atom or has 6 to 12 carbon atoms and optional substituted arylidene, and R
8Represent hydrogen, COOH, have the alkyl of 1 to 10 carbon atom or have 6 to 12 carbon atoms and optional substituted aryl.
The reaction of polyvinyl alcohol and compound (4b) is preferably carried out at least a inert solvent, and wherein term " inert solvent " is even be interpreted as it is all not disturb the solvent that stops the ideal reaction process under each reaction conditions.Special in this article ideal solvent is a water.
Wherein, reaction can more advantageously be carried out under the condition that an acidic catalyst exists.Suitable acid had both comprised organic acid such as acetic acid, comprised mineral acid example hydrochloric acid, sulfuric acid and/or nitric acid again, and used hydrochloric acid, sulfuric acid and/or nitric acid to prove specially suitable industrial.Reaction is preferably carried out as follows, is about to polyvinyl alcohol and inserts in the aqueous solution, compound (4b) is joined also then drip an acidic catalyst in this solution.
In the scope of first kind of embodiment of the present invention, obtain crosslinked polyvinyl acetal by carrying out following operation in any order,
(i) polymkeric substance (A1) and at least a polyacetals reaction with formula (5) and
R
9(CHO)
n (5)
The (ii) group of interesterification formula (1) and formula (4a) at least in part.
R wherein
9Expression singly-bound or have the group of 1 to 40 carbon atom, be preferably have 1 to 20 of ideal, preferred 1 to 12, the aliphatic series of preferred especially 2 to 10 carbon atoms, alicyclic and/or aromatic group.
Index n is the integer more than or equal to 2, preferably 2 to 10, more preferably 2 to 6, in 2 to 3 scope.According to a particularly preferred embodiment of the present invention, n is 2.
The compound that is particularly suitable for formula of the present invention (5) comprises glyoxylyl, mda, positive suceinic aldehyde, glutaraldehyde, positive hexanedial, positive heptan dialdehyde, positive suberic aldehyde, positive azel aldehyde, positive decanedial, n-undecane dialdehyde, n-dodecane dialdehyde, 4,4 '-ethylene oxo, two phenyl aldehydes and 2-hydroxyl hexanedial, preferred especially glutaraldehyde and positive azel aldehyde.
In category of the present invention, the amount of polyacetals (5) can be selected arbitrarily in principle, but is the object of the invention, especially preferably in the gross weight of polymkeric substance (A1), use 0.001 to 1.0 weight %, comparatively rational 0.005 to 2.0 weight %, the especially polyacetals of 0.01 to 1.0 weight % (5).
Step (i) and (ii) can carrying out with random order, promptly step (i) step (ii) step (i) secondly of step (ii) or at first secondly at first also can be carried out two steps simultaneously.But be the object of the invention, verified is at first to carry out step (i) secondly to carry out step (ii) especially valuably.
In particularly preferred embodiment category of the present invention, also can be added at least a compound at any time with formula (6).
Radicals R
10And R
11Be hydrogen independently of each other separately, have the alkyl of 1 to 10 carbon atom or have the aryl of 6 to 12 carbon atoms.Wherein, these alkyl and aryl can be by one or more hydroxyls, and sulfonic group and/or halogen atom such as fluorine, chlorine, bromine, iodine replace.Belong to formula (6) preferred compound be, formaldehyde, acetaldehyde, propionic aldehyde, butyraldehyde-n, isobutyric aldehyde, 2-oxyethyl group butyraldehyde, paraldehyde, 1,3,5-three alkane, hexanal (Capronaldehyd), 2-ethyl hexanal, aldehyde C-9,3,5,5-trimethylammonium hexanal, 2-formyl-Phenylsulfonic acid, acetone, ethyl methyl ketone, n-Butyl ethyl ketone and/or ethyl hexyl ketone.
In category of the present invention, the verified aldehyde that especially preferably uses, i.e. R in the formula (6)
10=hydrogen and R
11The compound of=hydrogen, methyl, ethyl, n-propyl or sec.-propyl preferably uses formaldehyde and/or butyraldehyde-n, especially preferably uses butyraldehyde-n.
The ratio of composition (5) and (6) is preferably selected by following
At least a compound (6) of (1) 95.00 to 99.99 weight parts,
At least a polyacetals (5) of (2) 0.01 to 5.00 weight parts,
Wherein said weight part preferably will be supplied 100.00 weight parts.
Polymkeric substance (A1) preferably carries out at least a inert solvent with the reaction of compound (5) and/or (6), and wherein term " inert solvent " is even be interpreted as it is all not disturb the solvent that stops the ideal reaction process under each reaction conditions.Special in this article ideal solvent is a water.
In addition, reaction can more advantageously be carried out under the condition that an acidic catalyst exists.Suitable acid had both comprised organic acid such as acetic acid, comprised mineral acid example hydrochloric acid, sulfuric acid and/or nitric acid again, and used hydrochloric acid, sulfuric acid and/or nitric acid to prove specially suitable industrial.Reaction is preferably carried out as follows, is about to polymkeric substance (A1) and inserts in the aqueous solution, joins compound (5) and/or (6) in this solution and then drips an acidic catalyst.
In second kind of embodiment category of the present invention, obtain crosslinked polyvinyl acetal by following operation,
(i) polymkeric substance (A2) and at least a compound reaction with formula (6),
(ii) add the compound of at least a formula (4b),
(iii) the polyacetals of adding type (5) and
(iv) interesterification formula (1) and derived from the group of the structural unit of formula (4b) compound at least in part.
Wherein, the compound such as the preceding definition that have formula (4b), (5) and (6).
Esterification process (ii) and/or (iv) simply mode carry out, but in category of the present invention, confirm, have under the condition of at least a tenderizer particularly preferably in optional, and under 80 to 280 ℃, preferred 120 to 280 ℃, preferred especially 140 to 260 ℃ temperature of charge, carry out the heat cross-linking process.
But can use the known heating installation of all technician, carry out the heat cross-linking of polyvinyl acetal as stove, kneader, forcing machine, moulding press or autoclave.But preferably in forcing machine or kneader device, carry out the heat cross-linking process, because they can guarantee to mix well with the tenderizer that is contained in a preferred embodiment.Wherein, by comparing with uncrosslinked polyvinyl acetal, crosslinked polyvinyl acetal has this phenomenon of higher molecular weight, and can pick out this cross-linking process.
Degree of crosslinking can choose at random---according to application target---.But preferred especially in category of the present invention, at least 10mol%, preferred 20mol% at least, more preferably all carboxyls that were contained in originally in the polyvinyl acetal of 30mol%, preferred especially 40mol% at least are esterified at least.Wherein, the content of carboxyl is with total restatement of crosslinked polyvinyl acetal, preferably smaller or equal to 10.0 weight % and more preferably at 0.00001 to 10.0 weight %, particularly preferably in 0.01 to 5.0 weight %, extremely preferred in the scope of 0.01 to 2.0 weight %.
In a preferred embodiment, cross-linked pioloform of the present invention contains tenderizer.What be used as tenderizer can be the known tenderizers of all technician.Tenderizer can use by the known convention amount of technician.The known polyvinyl acetal that is applicable to, the tenderizer that is specially adapted to polyvinyl butyral acetal is the ester of mono carboxylic acid of aliphatic series and dicarboxylic acid and monohydroxy-alcohol or polyvalent alcohol or oligo alkylene glycols ether, phosphoric acid ester and various phthalic ester, for example those disclosed in US-A5137954.But preferably use two, three and the diester of TEG and mono carboxylic acid of aliphatic series, the dibenzoate of hexanodioic acid dialkyl and alkylene glycol of in not shifting to an earlier date disclosed DE-A-10100681, putting down in writing and polyalkylene glycol.
The possible Application Areas of cross-linked pioloform of the present invention is that technician institute is conspicuous.They are specially adapted to the application scenario of all previous just cross-linked pioloforms on the books, particularly polyvinyl formal and/or polyvinyl butyral acetal.Particularly preferred Application Areas comprises it as film, the purposes of the film of laminated glass-use particularly, and they preferably can make by directly extruding by means of wide seam nozzle.Other detailed content about polyethylene extrusion acetal and preparation polyvinyl acetal film, particularly polyvinyl butyral film is that the technician is fully known from technical literature.
Within the scope of the present invention, a particularly preferred Application Areas of polyvinyl acetal of the present invention is the plane constituting body, particularly preferably has the film of 0.5 μ m to 1mm thickness.Can also contain other conventional additive in the film of the present invention, as oxidation stabilizer, UV stablizer, pigment, filler, pigment and/or antisticking agent.
In addition, polyvinyl acetal of the present invention also is specially adapted to coated substrate, particularly timber, metal, plastics, glass, fabric, paper, leather and pottery and mineral substrate.Therefore, content of the present invention also is to contain the coating of polyvinyl acetal of the present invention.
Also can contain fluoropolymer resin, tenderizer, pigment, filler, stablizer, bonding activator, auxiliary rheological agents in the coating in addition, influence the pH value additive and/or can catalysis polyvinyl acetal of the present invention and other fluoropolymer resin between and the additive of other fluoropolymer resins chemical reaction each other.
Coating procedure of the present invention both can with currently known methods with and then and preferred under comparatively high temps fusion and crosslinked powder type carry out, also can preferably carry out by the known coating process of technician with the form of organic solution.In the process that applies by solution, preferably will be with crosslinked polyvinyl acetal and other binding agent of choosing wantonly and other optional component treated of the present invention, be dissolved in together in solvent or the solvent mixture as tenderizer, pigment, filler, stablizer, bonding activator, auxiliary rheological agents, be applied over then on the base material to be coated.Preferably after boiling off solvent, under 20 to 200 ℃ temperature, carry out cross-linking process of the present invention ideally.Wherein, can reduce the interpolation of pH value such as the carrying out that organic and/or mineral acid helps crosslinking reaction.
If when being applied in the coating, compare with uncrosslinked polyvinyl acetal, cross-linking process can bring the raising of coating solvent resistance and the increase of molecular weight.
According to a further aspect of the invention, polyvinyl acetal of the present invention is applicable to that especially also the middle layer that preparation has an ionic conduction ability is used for the electrochromism system.
Claims (15)
1. method for preparing cross-linked pioloform, wherein need polymkeric substance (A1), and this polymkeric substance contains with lower unit in its gross weight:
A) the structural unit of 1.0 to 99.9 weight % with formula (1)
R wherein
1Expression hydrogen,
B) structural unit of the formula of 0 to 99.0 weight % (2)
R wherein
2Expression methyl or ethyl,
C) structural unit of the formula of 0 to 70.0 weight % (3)
R wherein
3, R
4, R
5And R
6Be hydrogen separately independently of each other,
D) structural unit of the formula of 0.00001 to 30.0 weight % (4a)
R wherein
7Be singly-bound, and R
8Be hydrogen,
It is characterized in that, carry out following steps in any order,
(i) polymkeric substance (A1) and at least a polyacetals reaction with formula (5),
R
9(CHO)
n (5)
Its expression glutaraldehyde and/or positive azel aldehyde and
The (ii) group of interesterification formula (1) and formula (4a) at least in part.
2. the method for claim 1 is characterized in that, is added at least a compound with formula (6) at any time,
R wherein
10And R
11Be hydrogen independently of each other separately, have the alkyl of 1 to 10 carbon atom or have the optional substituted aryl of 6 to 12 carbon atoms.
3. the method for preparing cross-linked pioloform, wherein want cross-linked polymer (A2), and this polymkeric substance contains with lower unit in its gross weight:
A) the structural unit of 1.0 to 99.9 weight % with formula (1)
R wherein
1Expression hydrogen,
B) structural unit of the formula of 0 to 99.0 weight % (2)
R wherein
2Expression methyl or ethyl,
C) structural unit of the formula of 0 to 70.0 weight % (3)
R wherein
3, R
4, R
5And R
6Be hydrogen separately independently of each other,
It is characterized in that,
(i) polymkeric substance (A2) and at least a compound reaction with formula (6),
R wherein
10And R
11Be hydrogen independently of each other separately, have the alkyl of 1 to 10 carbon atom or have the optional substituted aryl of 6 to 12 carbon atoms,
(ii) add at least a compound with formula (4b),
R wherein
7Expression singly-bound, and R
8Expression hydrogen,
(iii) add polyacetals with formula (5),
R
9(CHO)
n (5)
Its expression glutaraldehyde and/or positive azel aldehyde and
(iv) interesterification formula (1) and derived from the group of the structural unit of formula (4b) compound at least in part.
4. each described method among the claim 1-3 is characterized in that, uses butyraldehyde-n as compound (6).
5. each described method among the claim 1-3 is characterized in that, uses
At least a compound (6) of (1) 95.00 to 99.99 weight parts,
At least a polyacetals (5) of (2) 0.01 to 5.00 weight parts,
Wherein said weight part will be supplied 100.00 weight parts.
6. each described method among the claim 1-3 is characterized in that, is carrying out esterification process under the optional condition that has an at least a tenderizer and under in 80 to 280 ℃ the temperature of charge (ii) or (iv).
7. method as claimed in claim 6 is characterized in that, carries out cross-linking process in forcing machine, kneader device or other heatable equipment.
8. the cross-linked pioloform that obtains by each described method among the claim 1-7.
9. polyvinyl acetal as claimed in claim 8 is characterized in that, in the gross weight of polyvinyl acetal, its esterification with nonesterified total amount smaller or equal to 10.0 weight %.
10. polyvinyl acetal as claimed in claim 8 or 9 is characterized in that wherein containing tenderizer.
11. contain moulded piece just like each described polyvinyl acetal in the claim 8 to 10.
12. contain film just like each described polyvinyl acetal in the claim 8 to 10.
13. film as claimed in claim 12 is used to prepare the purposes of laminated safety glass.
14. contain coating just like each described polyvinyl acetal in the claim 8 to 10.
15. as each described polyvinyl acetal in the claim 8 to 10 be used to prepare that the electrochromism system is used, have a purposes in the middle layer of ionic conduction ability.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10300321 | 2003-01-09 | ||
| DE10300321.5 | 2003-01-09 | ||
| DE10319201.8 | 2003-04-29 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1759125A CN1759125A (en) | 2006-04-12 |
| CN100343288C true CN100343288C (en) | 2007-10-17 |
Family
ID=32519690
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2003801101334A Expired - Fee Related CN100343288C (en) | 2003-01-09 | 2003-12-12 | Crosslinked polyvinyl acetals |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN100343288C (en) |
| DE (1) | DE10319201A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108148156B (en) * | 2017-12-27 | 2020-10-30 | 吉晟光电（深圳）有限公司 | Polyvinyl butyral-based modified polymer and application thereof |
| CN110358341B (en) * | 2019-06-24 | 2021-08-10 | 中国路桥工程有限责任公司 | Spray film waterproof material and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4350773A (en) * | 1979-08-14 | 1982-09-21 | Mitsubishi Chemical Industries, Limited | Weakly acidic cation exchange resin and process for producing same |
| EP0211818A1 (en) * | 1985-07-02 | 1987-02-25 | Monsanto Company | Cross-linked polyvinyl butyral |
| CN1043509A (en) * | 1988-10-26 | 1990-07-04 | 阿纳托利·雅科夫列维奇·索罗金 | Produce the method that embeds vinyl alcohol and vinyl acetate copolymer that glutaraldehyde is arranged |
| US5332774A (en) * | 1992-10-16 | 1994-07-26 | Arco Chemical Technology, L.P. | Polyvinyl acetal resins based on hydroxyaldehydes and use of the resins in laminar structures |
-
2003
- 2003-04-29 DE DE10319201A patent/DE10319201A1/en not_active Withdrawn
- 2003-12-12 CN CNB2003801101334A patent/CN100343288C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4350773A (en) * | 1979-08-14 | 1982-09-21 | Mitsubishi Chemical Industries, Limited | Weakly acidic cation exchange resin and process for producing same |
| EP0211818A1 (en) * | 1985-07-02 | 1987-02-25 | Monsanto Company | Cross-linked polyvinyl butyral |
| CN1043509A (en) * | 1988-10-26 | 1990-07-04 | 阿纳托利·雅科夫列维奇·索罗金 | Produce the method that embeds vinyl alcohol and vinyl acetate copolymer that glutaraldehyde is arranged |
| US5332774A (en) * | 1992-10-16 | 1994-07-26 | Arco Chemical Technology, L.P. | Polyvinyl acetal resins based on hydroxyaldehydes and use of the resins in laminar structures |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1759125A (en) | 2006-04-12 |
| DE10319201A1 (en) | 2004-07-22 |
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