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CN1878803A - Products resulting from polymer-analogous reactions - Google Patents

Products resulting from polymer-analogous reactions Download PDF

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Publication number
CN1878803A
CN1878803A CNA2005800012173A CN200580001217A CN1878803A CN 1878803 A CN1878803 A CN 1878803A CN A2005800012173 A CNA2005800012173 A CN A2005800012173A CN 200580001217 A CN200580001217 A CN 200580001217A CN 1878803 A CN1878803 A CN 1878803A
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Prior art keywords
ketone
component
alkyl
polymer
products resulting
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Inventor
P·格勒克纳
F·G·施米德特
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Evonik Operations GmbH
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Degussa GmbH
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G6/00—Condensation polymers of aldehydes or ketones only
    • C08G6/02—Condensation polymers of aldehydes or ketones only of aldehydes with ketones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/38—Block or graft polymers prepared by polycondensation of aldehydes or ketones onto macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/02—Condensation polymers of aldehydes or ketones only
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Paints Or Removers (AREA)

Abstract

The invention relates to products resulting from polymer-analogous reactions of products comprised of aldehydes and ketones and of radically polymerizable monomers, to a method for the production thereof and to their use.

Description

Products resulting from polymer-analogous reactions
The present invention relates to products resulting from polymer-analogous reactions, prepare their method and their purposes.
EP 0 346 788, described radiosensitive compound among EP 0 377 199 and the DE 102 06 987, and it can contain the phenyl methyl ketone as subdivision (submoiety) if necessary, and/or has the polymeric derivative of phenyl methyl ketone part.
But EP 0 346 788 has described the unsaturated copolymerization of ethylene linkage, radiosensitive organic compound, and it has at least one (methyl) acrylate group.EP 0 377 199 has described the UV-cross-linkable composition based on (methyl) acrylate copolymer.The vinyl ether derivative has been described among the DE 102 06 987.
All do not mention type of polymerization in these documents by the ketone resin that contains phenyl methyl ketone of radical polymerization.
Ketone resin is for example being used in the coating as the resin that adds, so that improve some performance such as glossiness, hardness or mar-resistance.
Ketone resin has hydroxyl and therefore only can be crosslinked with for example poly-isocyanide ester or aminoresin usually.These crosslinking reactions are usually by thermal initiation or acceleration.Other functional group for example amino and/or carboxylic group can only introduce by special monomer, even and described monomer is available really, but they also are difficult to obtain with technical scale.
Die Angewandte Makromolekulare Chemie, 168 (1989), the type of polymerization of cyclohexanone-formaldehyde resin and azo-compound has been described in p.129ff..This method is expensive and difficult for technical scale.Since used azo-compound, its preparation is inevitable with great security burden so.In addition, azo-compound is heat-labile, and this causes storing expensive and difficult.
Journal of Applied Polymer Science, Vol.72 (1999) has described pimelinketone-and phenyl methyl ketone-formaldehyde resin in p.927ff., and it becomes photosensitive owing to the st-yrax that has added 10mol% or st-yrax butyl ether.Should synthetic be expensive and difficult, and need carry out plural step, and continue above 16 hours.Transform fully and can not be guaranteed, and may have the easy volatile composition.In addition, low molecular weight part has reduced the performance of high grade paint aspect mechanical properties.In addition, it has only been described with vinylbenzene as monomeric products resulting from polymer-analogous reactions.It is insufficient containing the weathering resistance of cinnamic polymkeric substance known.
An object of the present invention is to prepare the product of ketone resin and unsaturated monomer, described product also contains other functional group except that carbonyl and hydroxyl, and it is characterized by to compare with initial resin and have different solvabilities.
Another object of the present invention is a kind of method for preparing them of exploitation, and it can make above-mentioned performance change in a simple manner and greatly.
This product should be suitable for coating, tackiness agent, ink and comprise printing ink, jelly paint, rumbling compound, glaze, pigment paste, filler, makeup, sealing agent and/or insulating material.
Surprised is, can reach this purpose according to the type of polymerization of claim by ketone resin that contains phenyl methyl ketone and/or acetophenone derivative under the UV rayed and unsaturated monomer.
Suitable ketone resin is the polymeric reaction product of the ketone of the aldehyde of general formula I and general formula I I, can use additional ketone if desired.
Figure A20058000121700071
Wherein R=H has the not cladodification of 1-12 carbon atom or the alkyl of cladodification, aryl
R wherein 1=have an alkyl of the not cladodification of 1-12 carbon atom
Figure A20058000121700073
R wherein 3-R 7=H, alkyl, OCH 3, OC 2H 5, Cl, F, COO (C 1-C 3Alkyl).
In addition, R 4-R 6Can be OH, SH.
Suitable unsaturated monomer be can radical polymerization all unsaturated monomers.
Therefore the invention provides polymeric reaction product, it contains the reaction product of following component in fact
A) aldehyde of general formula I
Figure A20058000121700081
Wherein R=H has the not cladodification of 1-12 carbon atom or the alkyl of cladodification, aryl and
B) ketone of at least a general formula I I
Figure A20058000121700082
R wherein 1=have 1-12 carbon former in the alkyl of not cladodification
Figure A20058000121700083
Radicals R wherein 3-R 7=H, alkyl, OCH 3, OC 2H 5, Cl, F, COO (C 1-C 3Alkyl), R 4-R 6Can be OH in addition, SH and
C) if necessary, the acid ketone of a kind of additional C H-and
D) unsaturated monomer of at least a free redical polymerization,
It is used for coating, tackiness agent, ink as a kind of composition main, basic or that add and comprises printing ink, jelly paint, rumbling compound, glaze, pigment paste, filler, makeup, sealing agent and/or insulating material.
The aldehyde component A of suitable formula I) comprises the aldehyde of cladodification not or cladodification substantially, for example formaldehyde, phenyl aldehyde, acetaldehyde, butyraldehyde-n and/or isobutyric aldehyde, valeral and dodecanal.Usually can use described in the literature suitable all aldehyde of ketone resin synthetic.Yet preferably be used alone or as a mixture formaldehyde and phenyl aldehyde.
Required formaldehyde is about the aqueous solution or alcoholic solution (for example, methyl alcohol or the butanols) use of 20 weight %-40 weight % usually with concentration.Other form of formaldehyde, the use of for example right-formaldehyde or three  alkane equally can.
The ketone B of formula II) example is phenyl methyl ketone and cyclosubstituted acetophenone derivative, as hydroxyl-, methyl-, ethyl-, the tertiary butyl-and cyclohexyl-phenyl methyl ketone.
In addition, except B component), can also there be other ketone C individually or with form of mixtures in the mixture), as acetone, 4-tert-butyl methyl ketone, methyl naphthyl ketone, hydroxyl naphthyl ketone, methyl ethyl ketone, 2-heptanone, propione, methyl iso-butyl ketone (MIBK), Propiophenone, cyclopentanone, cyclododecanone, 2,2,4-and 2,4,4-trimethylammonium cyclopentanone, suberone and cyclooctanone, pimelinketone and have the pimelinketone that one or more all alkyl that contain the alkyl group that adds up to 1-8 carbon atom replace.The example of the pimelinketone that the alkyl that can mention replaces comprises uncle 4--amyl group pimelinketone, the 2-second month in a season-butyl cyclohexanone, 2-tert-butyl pimelinketone, 4-tert-butyl pimelinketone, 2-methylcyclohexanone and 3,3,5-trimethylcyclohexanone.
St-yrax and/or benzoic alkyl oxide such as methyl, ethyl, propyl group and isobutyl ether can be used as component C with the less content that mostly is most 9.9mol%), based on the ketone component.
Yet, in general, can use synthetic and all ketones of ketone resin synthetic of the suitable ketone resin described in the document, the acid ketone of more all CH-is used as additional ketone C).
Preferably formaldehyde and/or phenyl aldehyde and phenyl methyl ketone, hydroxyl-, methyl-, tert-butyl-and/or cyclohexyl-phenyl methyl ketone, if necessary, with 4-tert-butyl methyl ketone, pimelinketone, 4-tert-butyl pimelinketone, 3,3, the reaction product of 5-trimethylcyclohexanone and/or heptanone.
By component A), B), if necessary and C) preparation synthesizing in alkaline medium of polymkeric substance carry out (Dieter Stoye, Werner Freitag by condensation reaction in the mode known to from document, Lackharze, Chemie, Eigenschaften undAnwendungen, Carl Hanser Verlag, Munich, Vienna, 1996, p.164ff.; US-B2 540 885; US-B2 540 886; DB-C11 55 909; DL-PS 12 433; DE-C 13 00 256; DE-C 12 56 898; DE 33 24 287; DE103 38 580.0; EP 0 007 106; DE 12 65 415).
Reaction conditions:
Solvent:
Reaction can be used secondary solvent and carry out.Proved those suitable examples and comprised alcohol, as methyl alcohol or ethanol.Also can use water-soluble ketone as secondary solvent, for example methyl ethyl ketone or acetone, they go into resin by reaction bonded subsequently.
Alkali:
The present invention based on A), B), if necessary and C) product prepare by at least a alkali that uses 0.05-10mol% (based on employed ketone).(metal) oxyhydroxide preferably, for example positively charged ion is NH 4, Li, Na and K oxyhydroxide.Especially preferably use potassium hydroxide and/or sodium hydroxide.
The ratio of keto-aldehyde component:
Ketone component ((B) and total amount C)) and aldehyde component A) between ratio can be 1: 0.9-1: change between 4.But preferred ketone/the aldehyde ratio is 1: 1-1: 2.5.Ketone component and aldehyde component can be with pure form or form in aforesaid solvent or the addings of the form in water.Especially preferably use the aqueous solution or the alcoholic solution of formaldehyde, three  alkane and/or right-formaldehyde and/or phenyl aldehyde.
Ketone B) with component C) ratio:
Based on employed ketone B) and total amount C), the ketone B component) can there be preferred 20-100mol%, more preferably 25-100mol% with the scope of 10-100mol%.Ketone component C) can in the scope of 0-90mol%, use preferred 0-80mol%, more preferably 0-75mol%.
Can change performance in a simple manner by component kind and ratio each other, as the solvability in the opposed polarity solvent, with the consistency of other raw material, softening range, second-order transition temperature or other functionality are as the OH group.
A), B), if necessary and C) irradiation and the component D of reaction product by UV light) carry out similar polymeric reaction.
Suitable component D) be generally can radical polymerization all unsaturated monomers.
Preferably use toxilic acid, fumaric acid, vinylformic acid and/or methacrylic acid, methacrylic acid and/or acrylic acid C individually or with the form of mixture 1-C 40Alkyl ester and/or cycloalkyl ester, acrylic acid hydroxy alkyl ester and/or hydroxyalkyl methacrylate, glycidyl methacrylate, glycidyl acrylate, 1,2-epoxy butylacrylic acid ester, 1,2-epoxy butyl methyl acrylate, 2,3-oxirane ring amyl group acrylate, 2,3-oxirane ring amyl group methacrylic ester, acroleic acid esterification polyethers, vinylbenzene and/or its derivative can exist with less degree in addition.Can also use similar acid amides.
That other is fit to is (methyl) acrylate chloride, (methyl) acryloyl isocyanic ester, α, alpha-alpha-dimethyl-3-pseudoallyl benzyl isocyanate ester, alkyl position have 1-12, preferred 2-8, more preferably (methyl) acryloyl alkyl isocyanate of 2-6 carbon atom, for example methacryloyl ethyl isocyanate or methacryloyl n-butyl isocyanate.
Also can use two-, three-and/or tetraacrylate as component D), form the product of cladodification in this case.Example is propylene glycol diacrylate (DPGDA) or tripropylene glycol diacrylate (TPGDA), hexanediyl ester (HDDA) and Viscoat 295, and can use all higher polyfunctional acrylates of the suitable free radical reaction described in the document.
A), B), if necessary and C) reaction product and unsaturated monomer D) ratio can be 99%: 1%-1%: 99%, preferred 99%: 1%-20%: 80%, more preferably 99%: 1%-40%: change between 60%, in mass.
Also can carry out A), B), if necessary with C) different reaction product and unsaturated monomer D) similar polymeric reaction.
According to component kind and ratio each other, component A related to the present invention), B), if necessary and C), also have D) reaction product have
0-200 ℃ melting range, preferred 30-150 ℃, more preferably 40-125 ℃,
The molecular-weight average of 300-100 000, preferred 400-10 000, more preferably 500-5000g/mol,
Colour less than 7 (Gardner, 50% in ethyl acetate) preferably less than 5, is more preferably less than 3,
The OH value of 0-250mgKOH/g, preferred 0-200mgKOH/g and
The acid number of 0-250mgKOH/g, preferred 0-200mgKOH/g.
The present invention also provides a kind of method for preparing polymeric reaction product, and described product contains the reaction product of following component in fact
A) aldehyde of general formula I
Wherein R=H has the not cladodification of 1-12 carbon atom or the alkyl of cladodification, aryl and
B) ketone of at least a general formula I I
Figure A20058000121700121
R wherein 1=have an alkyl of the not cladodification of 1-12 carbon atom
Radicals R wherein 3-R 7Be H, alkyl, OCH 3, OC 2H 5, Cl, F, COO (C 1-C 3Alkyl), R 4-R 6Can be OH in addition, SH and
C) if desired, the acid ketone of a kind of additional C H-and
D) at least a unsaturated monomer that can radical polymerization,
Wherein with A), B), if necessary and C) reaction product and component D) mix, react by the irradiation of UV light subsequently, preferably under the atmosphere of rare gas element.
The present invention based on the preparation of resin in melt or in the solution of appropriate organic solvent, carry out.
If desired, this reaction can be quickened by adding light-sensitive catalyst such as tertiary amine.
One preferred embodiment in, if necessary in the presence of appropriate catalyst, to A), B), if necessary and C) the solution of reaction product or melt in add component D).Be exposed to after this under the suitable radiation, preferably under the atmosphere of rare gas element.
If desired, existing solvent can be removed after reaction finishes, and obtains the powder or the melts of product of the present invention in this case usually.
By using polymerisable acid, as vinylformic acid, methacrylic acid, fumaric acid and/or toxilic acid, and in suitable neutralizing agent and after obtain the polymkeric substance of unhydrolyzed and dilutable water.Dilutable to water can obtain by using the monomer that for example has polyether group, sulfonate groups and/or amino equally, and is if necessary after with suitable neutralizing agent neutralization.
The present invention also provides product of the present invention to comprise purposes in printing ink, jelly paint, rumbling compound, glaze, pigment paste, filler, makeup, sealing agent and/or the insulating material as a kind of main, basic or composition of adding at coating, tackiness agent, ink.
Found based on its ratio of total composition at 5 quality %-80 quality %, preferred 10 quality %-70 quality %, more preferably 15 quality %-60 quality % are favourable.
About this point, also demonstrated product of the present invention different raw materials has been had very wide consistency and combination easily.
This coating, tackiness agent, ink comprise that printing ink, jelly paint, rumbling compound, glaze, pigment paste, filler, makeup, sealing agent and/or insulating material can also contain auxiliary agent and auxiliary material, for example, inhibitor, water and/or organic solvent, neutralizing agent, surfactant, Oxygen Scavenger and/or free-radical scavengers, catalyzer, photostabilizer, toner, thixotropic agent, anti-skinning agent, defoamer, static inhibitor, thickening material, thermoplastic additive, dyestuff, pigment, fire retardant, internal mold release, filler and/or whipping agent.
Product of the present invention has improved gloss, levelling property and the hardness that coating, tackiness agent, ink comprise printing ink, jelly paint, rumbling compound, glaze, pigment paste, filler, makeup, sealing agent and/or insulating material especially.Also observed improved binding property in some cases.
The following example is intended to further illustrate the present invention, but its range of application is not limited.
Embodiment
Embodiment 1: the preparation of reaction product
With the 600g phenyl methyl ketone, 108ml methyl alcohol, also under agitation in nitrogen, be heated to 50 ℃ in 200g Cavasol W 7 M (methylated beta-cyclodextrin derivative, Wacker, Burghausen (DE)) and 180g formalin (concentration is 30% in the water) three-necked flask of packing into.Adding 16g concentration is 25% sodium hydroxide solution, and the reaction mixture heating is high to 70 ℃.In 90 minutes, add 330g formalin (concentration is 30% in water), reaction mixture is heated to 95 ℃ afterwards, keep then refluxing 5 hours.
Isolate water from resin mutually, resin with 100 ℃ water washing to neutralization, and under reduced pressure and be up under 150 ℃ the temperature and from volatile matter, isolate.
Obtain faint yellow, clarification, frangible resin thus, it has 50% solubleness and has 48 ℃ softening temperature in methyl ethyl ketone, acetone, ethyl acetate and dimethylbenzene.The Gardner colour of the ethyl acetate solution of 50% concentration is 2.2.The OH value is less than 10mgKOH/g.
Is that 1: 1 Hydroxyethyl acrylate and methyl methacrylate mixes with prepared resin with 1: 4 ratio and ratio.As irradiation under atmosphere of inert gases and the result who subsequently volatile matter is removed, molecular-weight average is from about 700gmol -1Rise to about 2250gmol -1Its OH value is 137mgKOH/g.
Application Example
The reaction product of 10g embodiment 1 is dissolved in the 10ml butylacetate, and adds 5gVestanat IPDI (Degussa AG) and 0.1g dibutyl tin dilaurate.
Use drawing frame that this solution is coated on the sheet glass, and preserved 60 minutes down at 120 ℃.Previous soluble film no longer can be dissolved in butylacetate.

Claims (21)

1, a kind of products resulting from polymer-analogous reactions, its polymeric reaction product by the preparation of following component is formed A) aldehyde of general formula I
Wherein R=H has the not cladodification of 1-12 carbon atom or the alkyl of cladodification, aryl and
B) ketone of at least a general formula I I
R wherein 1=have an alkyl of the not cladodification of 1-12 carbon atom
R 2＝
Figure A2005800012170002C4
Radicals R wherein 3-R 7Be H, alkyl, OCH 3, OC 2H 5, Cl, F, COO (C 1-C 3Alkyl), R 4-R 6Can be OH in addition, SH and
C) if desired, the acid ketone of a kind of additional C H-and
D) unsaturated monomer of at least a free redical polymerization.
2, according to the products resulting from polymer-analogous reactions of claim 1, it is characterized in that separately or be used in combination formaldehyde, phenyl aldehyde, acetaldehyde, butyraldehyde-n and/or isobutyric aldehyde, valeral and dodecanal) as aldehyde component A.
3, according to the products resulting from polymer-analogous reactions of claim 1, it is characterized in that separately or be used in combination phenyl methyl ketone and cyclosubstituted acetophenone derivative) as the ketone B component.
4, according to the products resulting from polymer-analogous reactions of claim 3, it is characterized in that separately or be used in combination hydroxyl-, methyl-, ethyl-, the tertiary butyl-and cyclohexyl-phenyl methyl ketone as cyclosubstituted acetophenone derivative.
5, according to the products resulting from polymer-analogous reactions of claim 1, it is characterized in that separately or be used in combination acetone, 4-tert-butyl methyl ketone, methyl naphthyl ketone, hydroxyl naphthyl ketone, methyl ethyl ketone, 2-heptanone, propione, methyl iso-butyl ketone (MIBK), Propiophenone, cyclopentanone, cyclododecanone, 2,2,4-and 2,4,4-trimethylammonium cyclopentanone mixture, suberone, cyclooctanone, pimelinketone and have pimelinketone that one or more all alkyl that contain the alkyl group that adds up to 1-8 carbon atom replace as the acid ketone component of additional C H-C).
6, according to the products resulting from polymer-analogous reactions of claim 5, it is characterized in that separately or be used in combination uncle 4--amyl group pimelinketone, the 2-second month in a season-butyl cyclohexanone, 2-tert-butyl pimelinketone, 4-tert-butyl pimelinketone, 2-methylcyclohexanone and 3,3, the pimelinketone that the 5-trimethylcyclohexanone replaces as alkyl.
7,, it is characterized in that mostly being most the acid ketone component of the CH-C of 9.9mol% according to the products resulting from polymer-analogous reactions of claim 1,5 and 6) can replace with st-yrax or benzoic alkyl oxide.
8, according to any products resulting from polymer-analogous reactions in the aforementioned claim, it is characterized in that using the unsaturated monomer of free redical polymerization) as component D.
9,, it is characterized in that using toxilic acid, fumaric acid, vinylformic acid and/or methacrylic acid, methacrylic acid and/or acrylic acid C separately or with form of mixtures according to any products resulting from polymer-analogous reactions in the aforementioned claim 1-C 40Alkyl ester and/or cycloalkyl ester, acrylic acid hydroxy alkyl ester and/or hydroxyalkyl methacrylate, glycidyl methacrylate, glycidyl acrylate, 1,2-epoxy butylacrylic acid ester, 1,2-epoxy butyl methyl acrylate, 2,3-oxirane ring amyl group acrylate, 2,3-oxirane ring amyl group methacrylic ester, acroleic acid esterification polyethers are as component D), wherein also used vinylbenzene and/or its derivative and similar acid amides.
10, according to any products resulting from polymer-analogous reactions in the aforementioned claim, it is characterized in that using (methyl) acrylate chloride, (methyl) acryloyl isocyanic ester, α separately or with form of mixtures, alpha-alpha-dimethyl-3-pseudoallyl benzyl isocyanate ester, alkyl position have (methyl) the acryloyl alkyl isocyanate of 1-12 carbon atom such as methacryloyl ethyl isocyanate or methacryloyl n-butyl isocyanate as component D).
11, according to any products resulting from polymer-analogous reactions in the aforementioned claim, it is characterized in that using two-, three-and/or tetraacrylate as component D).
12, according to any products resulting from polymer-analogous reactions in the aforementioned claim, it is characterized in that using propylene glycol diacrylate (DPGDA), tripropylene glycol diacrylate (TPGDA), hexanediyl ester (HDDA) or Viscoat 295) as component D.
13, according to any products resulting from polymer-analogous reactions in the aforementioned claim, it is characterized in that A), B), if necessary and C) reaction product and unsaturated monomer D) ratio can be 99%: 1%-1%: change between 99%, in mass.
14, according to any products resulting from polymer-analogous reactions in the aforementioned claim, it is characterized in that component A), B), if necessary and C), also have D) polymeric reaction product have
0-200 ℃ melting range,
The molecular-weight average of 300-100000g/mol,
Colour less than 7 (Gardner, 50% in ethyl acetate),
The OH value of 0-250mgKOH/g,
The acid number of 0-250mgKOH/g.
15,, it is characterized in that the ketone component ((B) and total amount C)) and the ratio of aldehyde component are 1: 0.9-1: 4 according to any products resulting from polymer-analogous reactions in the aforementioned claim.
16, according to any products resulting from polymer-analogous reactions in the aforementioned claim, it is characterized in that total amount ((B) and total amount C)), the ketone B component based on employed ketone component) be equivalent to 10-100mol%.
17, a kind of method for preparing polymeric reaction product, described product contains the reaction product of following component in fact
A) aldehyde of general formula I
Wherein R=H has the not cladodification of 1-12 carbon atom or the alkyl of cladodification, aryl and
B) ketone of at least a general formula I I
Figure A2005800012170004C2
R wherein 1=have the alkyl and a R of the not cladodification of 1-12 carbon atom 2=
Figure A2005800012170005C2
Radicals R wherein 3-R 7Be H, alkyl, OCH 3, OC 2H 5, Cl, F, COO (C 1-C 3Alkyl),
R 4-R 6Can be OH in addition, SH and
C) if desired, the acid ketone of a kind of additional C H-and
D) unsaturated monomer of at least a free redical polymerization,
Wherein with A), B), if necessary and C) reaction product and component D) mix, react by the irradiation of UV light subsequently, preferably under inert gas atmosphere, and if necessary in the presence of appropriate catalyst.
18, according to the method for preparing polymeric reaction product of claim 17, it is characterized in that A), B), if necessary and C) reaction product in the presence of alkali, prepare.
19, according to the method for preparing polymeric reaction product of claim 17 or 18, it is characterized in that A), B), if necessary and C) reaction product and component D) in the solution of melt or suitable solvent, react.
20, comprise purposes in printing ink, jelly paint, rumbling compound, glaze, pigment paste, filler, makeup, sealing agent and/or insulating material as a kind of main, basic or composition of adding at coating, tackiness agent, ink according to the polymeric reaction product of any in the aforementioned claim.
21, according to the purposes of the polymeric reaction product of claim 20, wherein can be in addition separately or in conjunction with having one or more auxiliary agents and auxiliary material, inhibitor, water and/or organic solvent, neutralizing agent, surfactant, Oxygen Scavenger and/or free-radical scavengers, catalyzer, photostabilizer, toner, thixotropic agent, anti-skinning agent, defoamer, static inhibitor, thickening material, thermoplastic additive, dyestuff, pigment, fire retardant, internal mold release, filler and/or whipping agent.
CNA2005800012173A 2004-08-26 2005-07-28 Products resulting from polymer-analogous reactions Pending CN1878803A (en)

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