DE2062528A1 - Process for the production of optically crosslinkable polymers - Google Patents

Description

DR. M0LLER-BOR6 DI PL-PHYS. DR. M AN ITZ Dl PL-CH EM. D R. DEUFEL DIPL-ING. FINSTERWALD DI PL-1 N G. G RÄMKO W 2062528

PATENT LAWYERS

H DEL ίο ..

Lo / Sh - A 2135

Agency of Industrial Science & Technology 3-1, Kasumigaseki 1 chome, Ghiyoda-ku, Tokyo, Japan

Process for the production of optically crosslinkable polymers

Priorities:

Japan dated Dec. 19, 1969, No. 10274-5 / 69 Japan dated Dec. 19, 1969, No. 102746/69 Japan, December 25, 1969, No. 1455/70 Japan of December 25, 1969, No. 1456/70 Japan of April 14, 1970, No. 31827/70

The invention relates to a method for the production of optically crosslinkable polymers. In particular, the invention relates to a method for producing optical crosslinkable polymer by polymerizing a compound "which has a vinyl group and a photosensitive, unsaturated Has remainder, in the vicinity of a polymerization catalyst, whereby only the vinyl residue is polymerized »

It is well known that poly (vinyl cinnamate), poly (vinylbenzylidene acetophenone) sPolyCvinylchalcon) etc. photosensitive resins which are widely used as photoresist resins. These photosensitive resins were made

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Dr. MOIItr-lori Dr. Monitz Dr. Daufal ■ Dipl.-Ing. FiniUrwald Dlpl.-Ing. Grflmkow Iraumcriw.ig, Am Bürg.rparlc I 8 Munich 22, Robert Kodi-Slraß · 1 7 Stuttgart - Bad Cannilatt T «l.fon (0531) 73687 Τ · Ι · (οπ (0811) 22 51 10, 221569, Τ · Ι · χ 522050 mbpal MarktilraO · 3, Teltfon (0711) M7261

BATH

in that - as shown in the following equation, poly (vinyl alcohol) or poly (styrene) etc. are reacted as a backbone polymer with oinnamoyl chloride. However, it is customary for such a method to have disadvantages, namely that the photosensitive group cannot be 100 % introduced into the framework polymer and that the property of the polymer obtained is dominated by the property of the framework polymer. '

. Pyridine or HaOH)

CH ₂ - GH ^ _n + ClOCCH = CH-

. * ^CH 2 -

OCOCH = CH-

ilCl, 2

■ fCH ₂ - CH

COCH = CH-

(2)

Therefore a photosensitive polymer with better properties to obtain, x-weary the method, first a Moriomeres with a photosensitive residue and then polymerizing the synthesized monomer is considered. An attempt was made to use photosensitive resin directly synthesize by synthesizing vinyl cinnamate monomer and was polymerized. However, since, as shown in the equation (3), such polymerization is mainly one Eiagsdi-uss polymerization mechanism follows, remain only few cinnamic acid residues in the polymer as side chains

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back, and therefore the photosensitivity is low.

OH ₀ = CH ^d J 0000H = OH-

m / n ^ 5

11

000H = OH I.

^C 6 ^H 5

A new process for the production of a highly effective, photosensitive polymer has now been carried out Synthesis and polymerization of a vinyl monomer which has a photosensitive residue "has been found.

By association of cinnamic acid, styrylacrylic acid, or homologues thereof with vinyl phenol, isoalkenylphenol or W -Halogenalkylvinyläther and ether _t of this quantity by combining Hydroxybenzylidenacetophenon (hydroxychalcone) or homologues obtained with ^ -Halogenalkylvinyläthern, are synthesized as monomers and polymerized in the presence of various polymerization catalysts. In the case of using a cationic polymerization catalyst, the vinyl radical contained in these compounds is selectively polymerized as shown below, whereby linear polymers are obtained in high yield which quantitatively have photosensitive radicals on their side chains.These monomers can easily be copolymerized with other comonomers will·

In Palle the use of radical polymerization catalysts, a linear polymer is obtained if the conversion is less than 50% ". It has been found in this case that dl" Most of the photosensitive groups

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remain as side chains:

OHp = GX

^0H 2 - f

R R

where R denotes the following radicals: O-

OCOC (Y) = GH 4 CH = CH

OCh ₂ CH ₂ OCOC (Y) = CH 4 CH = CH

OCH ₂ GH ₂ ^ Λ-CO

CH = CH

OCH ₂ CH ₂

CH = CH 4

CO

Z or

In this way it is possible through homopolymerization to obtain a polymer which not only has a very uniform quality and high photosensitivity, but also has good physical / mechanical properties. It is also possible to use a polymer with versatile properties, since copolymerization can be carried out. When carrying out of investigations with the polymer from ß-Vinyloxyäthylcinnamat was z. B. found that the resolution thereof is below 1 µm, development is easy, and that a clear cropped image can be obtained. Furthermore, the relative sensitivity of the polymer is a degree of polymerization in the range from 500 to 2500 (average polymer weight / Fw) 2 to 6 times that of poly (vinylciiinamate) available on the market. To this Thus, a photosensitive resin having excellent properties can be produced by the aforementioned method

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OH! GIHAL

will. Since these resins have a high resolution, you can they are used in the areas of precision electronics as in the case of integrated Circuits (10) and integrated circuits with large Dimensions (LSI) j can be used.

The aim of the invention is. A method for the production of to provide photosensitive resin in which a compound having a vinyl double bond and a photosensitive, unsaturated bond when monomer is polymerized.

A further aim of the invention is to provide a method for production of photosensitive resins with various properties by adding the above monomer with a chain polymerizable monomers is copolymerized.

Furthermore, it is an object of the invention to provide a method for the synthesis of the above-mentioned compound which is a vinyl radical and a Has photosensitive, unsaturated group to deliver.

In the invention, the following compounds are used as a monomer which has a vinyl group and a photosensitive, has unsaturated group;

(I) esters of vinylphenol or isoalkenylphenol with cinnamic acid, Styryl acrylic acid and its derivatives and compounds similar thereto, as represented by the following chemical formula: (j

£ r \

R £ r \ - OCOC = OH 4r CII = CH Y

In the formula, R represents an alkenyl radical, Y a sensitizing radical Substituents and Z is a substituent which is inactive with respect to the phenolic hydroxyl radical or carboxylic acid chlorides and η is 0, 1 or 2;

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(II) Ό -Vinyloxyalkyl esters of cinnamic acid derivatives or styryl acrylic acid derivatives and compounds similar to these, as represented by the following chemical formula:

GH = CH ^ ζ ^

GH ₂ = CHO ■ £

In the formula, η represents the numbers 2 to 4-, X represents the sensitizing agent Substituents, Z is a phenolic hydroxyl radical or carboxylic acid chlorides inactive substituents and η represents 0, 1 or 2;

(III) C 1-4 vinyl oxyalkyl ethers of hydroxybenzylidene acetophenone derivatives and compounds similar to this, which are given by the following chemical formula: '

CH ₂ = CHO (CH _{2) m} O

_ CO £ CH = CH

In the formula, m contrast the numbers 2, 5 or 4 ·, Z with one phenolic hydroxyl radical or carboxylic acid chlorides in active substituents and η represents the numbers 1 or 2.

The monomer according to (I) can by reacting o ~, m- or p-vinylphenol or isopropenylphenol with chlorides of cinnamic acid, Styryl acrylic acid and homologues thereof. The reaction is one which occurs between a phenolic hydroxyl group and a carboxylic acid chloride as by reproduced the following chemical equation:

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+ CIOC-C = CH - ^ - CII = CL, _n Y

The reaction can take place without a catalyst or in the presence of basic catalysts such as PjiLdin or triethylamine " Room temperature.

The reaction proceeds either in the absence of a solvent or in the presence of such solvents as dioxane and dimethylformamide away. Moreover, the progress of the reaction can be appropriately controlled by cooling or heating the reaction system as required.

The compound shown under (II) can be according to the following two Methods are synthesized?

(CH ₂ ) _m X + X ¹ OC-C = CH

CH = CH

CH ₂ = CHO

OCOC-CH - £ CH

In the formula, X represents a halogen radical, Cl or Br, and X * OH or the total salt thereof, d. H. LiO, NaO, KO.

Although reaction (1) would proceed without a catalyst, the reaction is generally accelerated using a quaternary ammonium salt as a catalyst, which is prepared by mixing trialkylamines with lower alkyl halogen compounds. In particular, when X ^f a is OH, the amount of trialkylamine is greater than that of the lower alkyl halide compound, so that the equivalent for the formation of the quaternary ammonium salt is

109629/16 ^ 2 "

is stepped. When X ^{1 is} an alkali metal salt of OH, e.g. B. LiO, NaO or KO, an exactly equivalent amount can be used.

As a result, it becomes a mixture of quaternary ammonium salt and trialkylamines applied in the former case, and only the quaternary ammonium salt is used in the latter case. turns. In addition, the course of the reaction can be more appropriate Way by cooling or heating the reaction system, can be controlled according to requirements.

T OH ₂ = OHO 4 OH ₂ - ^ - OH + ZOO-O = CH * £ OH = OH

GH,

₂ = 0H0 · £ - CH ₂ - ^ - OGOO = CH 4 OH = OH

wherein Y, X, m and η have the same meanings as listed above own.

In this case, the reaction (2) proceeds smoothly when a basic catalyst such as pyridine or triethylamine, is applied, but it also proceeds without a catalyst. It can also use a solvent such as dioxane or dimethylformamide can be used, and the temperature control can be used as explained above.

GH ₂ = OHO 4 GH ₂

CH = OH

CO

0H _d

^r m

00-4 GH = OH

'n

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The compounds given by the formulas (3) and (4) xd are synthesized by adding 4-hydroxy- or ^ -'- hydroxy-benzylidene acetophenone or the alkali metal salts of sodium, potassium, lithium, etc. or similar compounds with ! J-haloalkyl vinyl ethers are implemented. This reaction runs either on its own or in polar solvents, such as Methanol, Äthanpl, dioxane or tetrahydrofuran, from. In this case, the reaction can be noticeable by adding a small amount Increased amount of quaternary ammonium salt to the solvent will. .

Have the compounds shown under (i), (II) and (III) a vinyl double bond and a photosensitive, unsaturated one Binding. The invention provides a photosensitive resin having a photosensitive unsaturated bond such as Side chain, by polymerizing only the vinyl radicals of the compound owns.

The polymers according to the invention can be synthesized by the two methods shown below:

(a) Homopolymerization of the through (I), (II) or (III) again given connections;

(b) Copolymerization of one represented by (I), (II) or (III) Monomers with at least one chain-polymerizable monomer.

Compounds such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, phenyl vinyl ether, styrene, methyl styrene, chlorostyrene, X, -methyl styrene, methyl acrylate, ethyl acrylate, hexyl acrylate, methyl methacrylate, butyl methacrylate, 2-ethylhexyl acrylate, vinyl chloride, vinyl fluoride, vinylidene chloride, vinyl nitride fluoride , Vinyl acetate, acrylamide, butadiene, chloroprene, isoprene, trioxane, tetraoxane, epichlorohydrin, ethylene oxide, propylene oxide, butylene oxide and tetrahydrofuran are used as the chain-polymerizable monomer.

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The copolymerization of these compounds can be carried out without a catalyst or in the presence of a cationic catalyst or a free radical catalyst. in the The following is a description of the polymerization in the presence of these catalysts

1) Cationic Polymerization

For this process, an initiator is used, which consists of one or more types of cationic Polymerisationsk is composed of catalysts, which from the group of irifluorobor or ether compounds thereof, tin tetrachloride, Aluminum chloride, aluminum sulfate, triethylaluminum chloride, Zinc chloride or sulfuric acid are selected »Although the amount of catalyst to be used is generally in the range from 10 ^ to 10 wt .-%, based on the monomer, is the preferred range is 10 "" to 5 wt%.

The polymerization reaction can be carried out in the absence of a solvent if the monomer used has a low melting point. In general, however, the polymerization is desirably carried out in a solvent. A mixed solvent-is for this purpose ψ applied tel, which consists of one or more varieties of opposite cationic polymerization 'inactive solvents, and, methylene chloride, ethylene chloride, nitromethane, carbon tetrachloride, nitrobenzene, Oyclohexan and η from the group of benzene, toluene -Hexane to be selected. The monomer concentration is generally in the range from 0.5 to 90% by weight, and preferably it is in the range from 3 to 70% by weight. In general, the polymer is in the range of -13O ionstemperatur "to 70 ⁰ C, with the preferred range is -80 ° to 40 ⁰ C.

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The polymerization is carried out in the usual manner, with particular care being taken to prevent access not to allow water to enter the reaction system. After the polymerization is complete, a small amount of ammonia, Pyridine or a similar, weakly basic substance is added to the polymerization solution to the catalyst to deactivate. The solution can be stored in its concentrated or unmodified state. on the other hand can it in alcohol or a similar non-solvent, which contains a small amount of the aforementioned weakly basic substance, must be poured in to make the insulation and to effect purification of the polymer.

2) Free radical polymerization

Radical polymerization is generally used for radical polymerization Polymerization catalyst such as azobisisobutyronitrile, phenyl azo triphenylethane, benzoyl peroxide, acetyl peroxide or Cumene hydroperoxide used. The amount of catalyst to be used is generally in the range from 0.01 to 10 wt. ~ S6, and preferably in the range from 0.1 to 5% by weight, based on the monomer. Although the polymerization reaction can be carried out in the absence of a solvent, it will generally preferred that it be carried out in solution.

For this purpose, a mixed solvent consisting of one or more kinds of solvents such as Benzene, toluene, tetrahydrofuran, dioxane, methyl ethyl ketone, Composed of dimethyl sulfoxide, dimethylformamide and chloroform which are generally used for radical polymerization ■. The monomer concentration is generally in the area. Tone 0.5 free 90 wt. $ 6, and preferably in the range from 1 to 80 wt .- ^. In the absence of solvent, the Polymerization temperature be at least the same or higher

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than the melting point of the monomer to be used. In the case of solution polymerization, however, the temperature is in the range from 10 to 200 ^° C., preferably from 30 to 150 ^° C. The polymerization is carried out in vacuo or in an inert gas, and in each case the polymerization is carried out within a range of .50 Wt% conversion stopped. The polymer is isolated and purified by pouring the polymerization solution into alcohol or another non-solvent of the same type.

The polymerization without the use of a catalyst is carried out either under completely the same conditions as in the case radical polymerization, except that the use of the catalyst is omitted. Solution polymerization is also in general in this case preferable.

Copolymerization method

The oleopolymerization method of (I), (II) or (III) The compounds shown with various chain-polymerizable monomers are generally the same as in the case of homopolymerization although the polymerization conditions are slightly variable with the polymerizability of the latter monomer. Hence the method of Homopolymerization can be applied to this copolymerization with the necessary modifications.

Since the homopolymers and copolymers produced in this way the structure of the photosensitive, unsaturated bond in the side chain of the molecule, as already explained, own, these products can be used as photosensitive resins, varnishes and paints, which are excellent Have properties that come from photosensitivity " which is inherent in this structure. In this. Trap can

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Photosensitivity of these substances further through incorporation well-known photosensitizers such as 5-nitroacenaphthene, Picramid, p, p'-tetramethylaminobenzophenone, each to be improved according to requirements.

In addition, the abovementioned monomers can also advantageously for modifying polymers in generally be applied.

Raw materials such as cinnamic acid and 2-chlorovinyl ether, which are used in the invention are manufactured on an industrial scale and can therefore be obtained at low cost will. The polymerization process according to the invention make it possible that the desired polymers are generally in in high yields, and they do not have difficult problems in terms of industrial application Episode.

The invention therefore provides a process for the preparation of photosensitive polymers without recourse to a high polymer reactor and therefore it is unique in this regard. Recently, a production method for photoempHndliehe resins was some cinnamic acid derivatives, which have a glycidyl ether by copolymerization described with alkylene oxides (US Patent 3 4-09593). However, the invention is not concerned with such reactions but involves an entirely new process for the preparation of photosensitive resins by using a number of derivatives as monomers of the photocyclobutane-forming type.

The following examples explain the invention in more detail, without to restrict them.

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Example 1 ; Preparation of 4-tinyl pkenyl cinnamate

12.00:; p-Viuylphenol and 19 ₅ g 9O Oinnaiaoylchlorid were added to 100 ml of pyridine. The mixture was stirred for 5 min at 50 ° C ^; heated, then b _t ei normal room temperature for 2 h and then allowed to stand at room temperature Sachtleben. The solution obtained resulted in the addition of a solution which contained 100 ml of concentrated hydrochloric acid diluted with 400 ml of water, a Hiedersohlag. The suggestion was separated off by filtration and washed with water. The precipitate was washed further with 500 ml of 5% cold sodium carbonate solution, then washed with water, dried under reduced pressure and then purified by uncrystallization using an n-IIescan. Yield = 20.72 g; Melting point = 101 to 102 ⁰ G.

Elemental analysis values for G ^ IiL ^ O ^ i Calculated: G = 81.58 % \ H = 5.64 % Found: C = 81.52%; H = 5.62 %

Example 2 : Preparation of 2-YinylpIiei ^ ylcinna.mat

A mixture with 2.40 g of o-vinylphenol and. 4.00 g of oinnanoyl chloride added to 20 µl of Pyrxdin vairda box normal room mp or attir stirred overnight. The solution was then treated in the same way as in Boiopiel 1. The product was recrystallized using n-IIorane. Yield = 3 »00 g; Sclimalzpunlct = 55 'to 56 ⁰ C.

Values of the elemental analysis for C ^ r-jH ^^ Op: Calculated: G = 81.58 % - _t II = 5.64 % Gofuiiden: C = 81.65%; H = 5.50%

Example 3 '< Preparation of 3-vinylphenylciniiamate

A mixture consisting of 2.40 g of m-vinylphenol and 4 ₅ 00 g Oinnamoylchlorid, added to 20 ml of pyridine was was

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the reaction and treatment in de,? in the same manner as in Example 2. The product was obtained by uakrystallization Purified using n-hexane. Yield = 4.11 g; Sch.jolnpunkt = 67 to 68 G.

Elemental analysis values for C ^, -, H ^ ^ O ^ ' Calculated: G = 81.53 % \ H = 5.64 ^c / o Found: G = 81.59 %; H = 5.65 / »

, Example 4 : Preparation of 4-isopropenylphenylcinnaate

A mixture consisting of 2.00 g of p-isopropenylphenol and 4.00 g of ginnamoyl chloride added to 20 ml of pyridine was examined for the reaction in the same manner as in Example 2j. After the completion of the reaction, the reaction solution was combined with a solution of 40 ml of acetic acid in 40 ml of water. The solution then gave a precipitate which was separated off by filtration and washed with water. The precipitate was washed further with 100 ml of 3% cold sodium carbonate solution, then washed with water, dried under reduced pressure and then purified by recrystallization with ethanol. Yield = 2.92 g; Melting point «* 108 to 110 ⁰ G.

Elemental analysis values on C ^ nEL ₆ O ₂ J Calculated: G = 81.79 % \ H = 6.10 % Found * G = 81.81 % \ H = 6.07 %

Example 5 '· Preparation of 4-vinylphenyl-4-nitrocinnamate

A mixture which is added to 25 ml of pyridine containing _3} 00 g of p-vinyl phenol and 6.83 g of p-Nitrocinhamoylchlorid, was subjected to reaction and treatment in the same manner as in Example. 1 The product was purified by recrystallization using ethanol. Yield "6.05 g""meltingpoint" 147 to 148 ⁰ O.

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Elemental analysis values for G / .Ji ^ ₇ OJSr: Calculated: G = 69.15 % \ H = 4.44 % \ N = '4.74% Found: C = 69.19%; H = 4.40%; N = 4.71 / o -

Example 6 : Preparation of 4-yinylpli3.nyl-3-nitrocinnariate

A mixture containing lots of 2.50 g of p-vinylphenol and 5.70 g of m-nitrocinnaiaoyl chloride added to 25 ml of pyridine was subjected to the reaction and treatment in the same manner as in Example 1. The product was through Purified recrystallization using ethanol. Yield = 5.09 g; Melting point = 89 to 90 ⁰ G.

^ We! "Te of the elementary analysis on C ^ r ₇ H ,, ^ 0 ^, N: Calculated: G = 69.15 %; H = 4.44 %; Ή = 4.74 ~, o Findings: G = 69.34%; H = 4.41%; N = 4.49 %

Example 7 > Preparation of 4-vinylphenyl-4-chlorocinnamate

A mixture containing 1.20 g of p-vinyl p] aenol and 2.41 g of p-glilorcinnamoyl chloride added to 15 ml of pyridine was subjected to the reaction and treatment in the same manner as in Example 1. The product was purified by recrystallization from ethanol. Yield = 2.49 g; Scliraelz- = 128 to 129 ⁰ O..

Elemental analysis values for C ^ nH ^^ OoGl: Calculated: G = 71.71%; H = 4.60% Found: G = 71.73 % -, H = 4.45 %

Example 8 : Preparation of 2-vinylplienyl-4-chlorocinnamate

In the same manner as in Example 1, the synthesis was carried out of 2.00 g of o-vinylphonol, 4.30 g of p-chlorocinnamoyl chloride and

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20 ml of pyridine carried out. The product was recrystallized using η-hexane. Yield = 3 »76 gj melting point = 78 Ms 79 ⁰ G.

Values of the elementary analysis for C ^ H ^ -zOpCl: Calculated: C = 71.71%>. H = 4.60 % Found: C »71.72 % \ H = 4.47%

Example 9 ? Manufacture of 3-vinylphenyl-4-chlorocinnamate

In the same manner as in Example 1, the synthesis was carried out of 2.00 g of m-vinylphenol, 4.30 g of p-chlorocinnamoyl chloride and 20 ml of pyridine carried out. The product was made using n-hexane recrystallized. Yield = 3.51 g> Melting point = 56 to

57 ⁰ G.. (

Elemental analysis values on CynEL ^ OpCl: Calculated: G = 71.71 % \ H = 4.60 % Found: C «71.53 % \ H - 4.46%

Example 10 : Preparation of 4-yynylphenyl-4-methoxycinnamate

In the same manner as in Example 1, synthesis was carried out on 1.20 g of p-vinylphenol, 2.36 g of p-methoxycinnamoyl chloride and 15 ml of pyridine. The product was recrystallized from ethanol. Yield = 2.24 g; Melting point = 129 to 130 ^° C. j

Elemental analysis values for C ^ gH ^ gO ,: Calculated: C ■ - 77.12 % \ H »5 * 75 % Found: C * 77.15 % \ H. - 5.54 %

Example 11 : Preparation of 3-vinylphenyl-4-methoxycinnamate

In the same way as in Example 1, the synthesis was of 1.20 g of m-vinylphenol, 2.36 g of p-methoxycinnamoyl chloride

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and 15 nl pyridine carried out. The product x-nir & e means n-Heran recrystallized. Yield = 2.10 g; Enamel,

point = 88 to 89 ⁰ C. '■ "

Values dor Elomutaraiialysis on CpH ^ O-,:

ι IO IO y

Calculated: C = 77.12%; Ii = 5.75% Found: .. C »77.2.1 % \ H = 5.72 %

Example 12 : Preparation of 4-vinylphenyl- ^ i-cyanocinnaiate

In the same manner as in Example 1, the synthesis was carried out on 2.00 g of p-vinylplienol, 4.40 g of O ^ i-Gyajiociixaamoylchlorid and JO ml of pyridine. The product -.rurde was recrystallized in ethanol. Yield = 4.22 g; Melting point 144 to 145 ⁰ G.,

Values of the elemental analysis to 0 ^ ρΗ ^^ 0 _ο ϊί:

Calculated: C = 78.53 % \ H = 4.76 $ b; Π = 5.09 %

Found: C = 78.53 % \ H = 4.57 % \ N »5.00 %

Example 13 'Preparation of 4-Isopropenylph.3rLyl - ^ - cyano-

cimiamat

A mixture containing 0.60 g of p-isopropenylphenol and 1.50 g of! ^ '- cyanocinnaLioylchloride added to 100 ml of pyridine was subjected to the reaction in the same manner as in Example-4 to prepare the product, yield β 1.36 g; Melting point = »103 to 105 ⁰ O.

Elemental analysis values on C ^ q

Calculated: C = 83.48%; H - 5.53 % \ N = 5.13 % Found: C β 83.41%; II =. 5.55 ^; Έ = 5.24%

Example 14 : Preparation of 4-vinylphenyl-ß-styryl acrylate A mixture containing 1.8 g of p-vinylpherol and 4.0 g of ß-styryl

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acryl 07I chi or id, L, ugasct ^ t vji 40 ill pyridine, was selected to 40 ⁰ G and 1.5 ^ in. movement £ eL.?. lten, then 2.5 h at normal or Zi :: r , kept moving at a certain pace and left claim to be left behind. 200 ml of water, which contained ¹ \ ml of concentrated sulfuric acid, were poured into the solution in EuIi3, and the precipitate ευ. cause. Dor ent was jiie l Tim ο d ei * impact was abgotronnt by filtration and washed -ait water "Precipitation x-mrde v / pus washed with 100 ral 3.0 ^ strength cold Hatriuincarbonatlösung, further washed with washer, gotrocknot under pressure and impeded then uncrystallized with alcohol for cleaning. Expansion = 3.5 SJ Schmel2puiü: t = 149.5 to 150.5 ⁰ G.

Values of the element ar analysis on G ^ qII ^ qO ^ s Bereclinet: C «. 82.68 % \ H = 5.84 % Found: 0 = 82.72 5 »; H = 5 * 83 %

Example 15 ? Production of 2-vinylphenylß-styryl acrylate

, V / urde heating a mixture which was added contained 1.8 g of o-Yinylphenol and 4, Og ß-Styrylacryloylchlorid to 40 ml of pyridine at 40 to 45 ⁰ C and 2 h kept moving and then allowed to stand room temperature Uachtbei . By treating the resting solution with a dilute solution of hydrochloric acid in the same manner as in Example 14, an oily precipitate was obtained. This oily substance, together with the supernatant liquid, was extracted twice with 50 ml of benzene. The extracted solution was washed twice with 5 ml of 3.0% cold sodium carbonate solution and further washed with water. The benzene solution was dried with anhydrous sodium sulfate and then concentrated to give a product in a crystalline form. This product was purified by recrystallization using n . -Eexan purified yield = 3.0 g; melting point of a 73; 1 to 74.5 ⁰ C.

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Values of the elemental analysis on CL ₀ EL _p Op:

Calculated: C = 82.68 % \ H = 5.84 % Found: G «82.86 #j ' H = 5.90 %

Example 16 : Preparation of 3-vinylphenyl-β-styryl acrylate

A mixture containing added containing 1.8 g of m-Viiiylphenol and 4.0 GSS Styrylacryloylchlorid to 40 ml of pyridine was heated to 40 ⁰ C and 3 h kept in motion, then overnight at normal room temperature allowed to stand. The procedure of Example 14 was then followed. The product was recirculated using II-hexane. Yield = 3.1 Sj Melting point: 66.5 to 67.8 ⁰ C.

Values of the element ar analysis on G ^ qILoOo: Calculated: G = 82.68%; II «5.84 % Found: G = 32.58 %; H = »5.83 %

Example 17 »Preparation of 4-Iaopropenylphenyl-βs t yryl ac r yl at

A mixture vj-hich 2.0 g of p-Isopropenylplienol and 4.2 g of ß-Styrylacryloylchlorid added to "and dissolved in 40 ml of pyridine containing, was heated to 50 ⁰ G and 2.5 h kept moving, then at normal "room temperature kept in motion for 4 hours and left to stand overhead.

By adding 200 ml of water, which contained 30 ml of glacial acetic acid, ZVL of the solution in the envelope, a ϊΓχο-i-jrschlag was added. The product was obtained by following the ArLsitswοίο3 of Example 14 from this point on. It wurde- "urcli Uiakristallisation using toluene purified Au ₁ Jb-rat ■: ■ = 3.4 g; Gclimelzpunl. T = ⁰ 163.5 to 165.2 C.

Values ? _: Ys: Zl. ^ M ^ .it ·? .Ϊ analysis on 'G ₀ ^ lIy, _Γ 0η' · lic, "■" ■ 'el ■■■ "': C = · 2 ¹ ^ ^{7 r} ü II = ~~? ^u 'ο

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Example 18 : Production of 4-vinylphenyl- λ'-cyano-ßstyrylacrylat

A mixture containing 1.8 g of p-vinylphenol and 4.4 g of Λ'-cyanoß-styrylacryloyl chloride added to 40 ml of pyridine was subjected to the reaction following the procedure of Example 14. The conversion product was by turnover. "stallisatioii cleaned with Benaol yield = 3.7 gj melting point = 172 to 173.5 ⁰ C

Values of the ElüBientar analysis on CpgH ,, JSOp:

Calculated: 0 = 79.72 ° / o \ Ii =. 5.02 %; N = 4.65 %

G-eftindeiii G = 80.73 foy H = 5.07 ° / o \ Ή = 4.54 %

Example 19 i Preparation of 2-vinylphenyl- '% -cyano-ßstyrylacrylat

n mixture containing 1.8 g of o-vinylphenol and 4.4 g of Λ-Oyanoß-styrylacryloja.chlorid, added to 40 ml of pyridine, Xijurde heated to 40 0 and kept in motion for 3 h and then left to stand over a fold. The reaction mixture was treated in the same manner as in Example 14 to obtain the product. This was purified by recrystallization from alcohol. Yield 3.4 g / melting point = * 145 to 146.8 ⁰ O.

i values of the elemental analysis on CoqEL j-NOo J

Calculate ^} C = 79.72 ^; H »5.02 ^ j N» 4.65 %

Found: G = * 80.21 % \ H = 4.86 fo; N «4.56 %

Example 20 : Preparation of 4-isopropenylphenyl- <> i-cyanoß-styryl acrylate

2.0 g of p-isoproponylphenol and 4.2 gyetyryl (i-? I-cyano) acrylic acid chloride was added to 40 ml of pyridine. Under loading

- 21 -

BATH

109829/1602

following; following the procedure of Example 14, the mixture was subjected to reaction and post-treatment. The product was purified by recrystallization with toluene. Yield = 3.6. si melting point = 164.5IiS 166.0 ⁰ C.

fourth of the element ar analysis on Go * H.,

Calculated: 0 = 79.95 % \ H = 5.43 % \ H = 4.44 % Found: G »80.09 % \ H = * 5.34 % \ U = 4.43 %

Example 21 : Production of β-vinyl ο sqyäthyl cinnamate

34.0 g sodium cinnamate, 1.0 g methyltriethylammonium iodide and 0.5 S hydroquinone were added to 180 ml of 2-chloroethyl vinyl- ■ ether added =. The resulting mixture was in In the state of movement maintained, boiled under reflux for 4 hours and then left to stand for 1 hour at normal room temperature «. The resulting precipitate was separated off by filtration and washed twice with 20 ml of 2-chloroethylphenyl ether, the washing liquids being combined with the mother liquor. The mother liquor was reduced under reduced Pressure concentrated to remove excess 2-chloroethyl vinyl ether to be obtained here and at the same time raw ß-Vinylo ^ yäthylcinnamat to win. This aiohe product was made by, under Purified distillation carried out under reduced pressure, yield> 40.4 g; Boiling point- »116 to 118 ° G / 0.05 mm Hg.

Values of the element ar analysis on C ,. JrI ^ O ,:

Calculated: G = 71.54 % \ H «6.47 % Found: G = 71.49 % \ H = 6.43 %

Example 22: Production of β-vinyloxyethyl cyanocinnamate

-Oi-

A mixture containing 19.5 S sodium / yanocinnamate ,. 0.5 S methyltriethylammonium iodide and 0.3 G hydroquinone, added cv. 100 ml of 2-chloroethyl vinyl ether was added with stirring

_. op _. ■

109829/1602

BATH ORIGINAL

4 l \ viite :? The reflux was closed and then left to stand for 1 hour at normal room temperature. The resulting precipitate ίπιγΟ.ο separated by E ¹ H tr ration va ± C. Dt. ^R eiiaal with 10 ml of 2-CiIlOrLVbIIyIViIIyIlVuIiOr gewaachen wherein AiG WascliflÜGsigkeiton nib eggs Iluttci'lauge combined vnirde_ ± "

By following the procedure of Example 21 of this Point on, the product was obtained. Yield = 19.9 SJ Boiling point = 137 Mc 139 ° C / 0.07 am Hg

Elementalysis values on ö- ^ H- t-iTO ₇ :

Calculated: 0 = 69.12 JOj H = 5.39 % \ N = 5.76 % Found: C = 69.19 % \ H = 5.32 #j N = 5.69%

Example 23 Production of β-Tinyloxyätliyl-3-Bietliylciraiamat

A mixture containing 8.8 g of 2-hydroxyethyl vinyl acetate? and 19.9 p

3 — M e t hvlj- / cinnamöyl chloride, added to 100 ml of pyridine, heated to 40 ° C. while being kept in motion and at Maintained this temperature for 2 hours and then left to stand overnight at normal room temperature »

The reaction product was sufficiently washed with water, to obtain an oily crude product. In the presence of 0.1 g of hydroquinone added for this purpose, the crude product is obtained

by distillation carried out under reduced pressure Ä

cleaned. Yield = 28.2 g; Boiling point = 123 to 127 ⁰ G / 0.4 ma ng.

Words of Elomontarano.lyüc on O ₇ J ₇ IL ^ O ₇ -:

Calculated: C β 71.54 #j II = 6.47 % on: 0 _e 71.60 #; II = 6.39 %

24 : IIo ^ rt-Gllimc. 'O. I? -Vi-: 7loryätjyl-ß-.jtyr7l ^ ci-ln.t

-IcL -.:; 9.3

ioei.s »mt> _βΛ0

Methyltriethylammoüiumgodid and 0.1 g hydroquinone, added to 50 ml of 2-chloroethyl vinyl ether contained ". was in motion maintained state refluxed for 5 h and then at left to stand for 1 hour at normal room temperature. The resulting precipitate is separated by filtration and twice gexjaschen with 10 ml of 2-chloroethylvin'yl ether, the washing liquids were combined with the mother liquor »by the subsequent implementation and post-treatment in the same In a manner as carried out in Example 21, the following product was obtained; Yield "= 9» 5 g; boiling point = 145 to 150 ° 0 / 0.2 mm Hg.

Values of the elemental analysis for C ^ iI-LqO ₇ : Calculated: C = 73.75 %, H. = 6.60 70 Found: C = 73.73 %; H = 6.51> *

Example 23 ' Production of 4- (ß-Vinyloxy) -ethoxy ~ benzylidene acetophenone (chalcon)

13? 5 ecm Natriummethorid methanol solution containing (in which Na 1ecm in an amount of 0.0763 g / of Natriummethoxides is contained) was added to 30 cc of methanol, dissolved in 10.0 g of 4-Hydro2cy-berizylidenacetophenon (4 ^t -Hydro2cychalcon.) Was added , and the methanol was then removed under reduced pressure. The product obtained was ground well to a fine powder, and 50 g of 2-chloroethyl vinyl ether and 0.5 g of methyltriethylammonium iodide were added. The mixture was refluxed with stirring for 2 hours. The solution obtained was filtered off with suction and filtered, and the sodium chloride obtained was separated off. The 2-chloroethyl vinyl ether remaining in the filtered solution was removed by distillation. After your. Dissolving in chloroform, the residue was washed twice with water and dried by adding sodium sulfate anhydride. The solvent was then removed and the crystals of 4 ^! ~ (ß-vinyloxy) '-'. tho :: yaceüoplienoü. were in a yield of 12, C3 g,.

- 2-Ί- -

109829/1602

The crystals of 4 ⁱ - (ß-vinyloxy) -ethoxy-benzylideneacetophenoii were recrystallized and purified by means of η-hexane-benzene mixture. Melting point = 87 to 88 O.

Values of the elemental analysis on C ^ qH ^ qO ^: Calculated: G = 77.53 ° / o \ II = 6.16 fo Geftmden: G = 77, fO ° / o \ II »6.15 %

Example 26 : Preparation of 4- (β-vinyloxy) ethoxybenzylidene acetophenone

This experiment was carried out in the same manner as in Example 25, except that 4-hydroxy-benzylidene acetophenone was replaced by 4-hydroxyl-benzylidene acetophenone. The crystals of, 4- (β-vinyloxy) -ätlioxy-benzylidene aootophenone were produced in this way in a yield of 11) 30 s. The crystals of 4- (β-Vinylox ^ -ethoxybenzylidene acetophenone were recrystallized and purified by means of a n-hexane-benzene mixture. Melting point - 92 to

V / er to the element ar analysis on O ^ nII ^ oO ,: Calculated: G = 77.53% i H = 6.16 % Found: C = 77.33 % \ Ti m 6.17 / °

Example 27 ; . "

1.00 g of 4-Viiiylphenylcinnamat viurden in 3j00 g Methyl _w enchlorid dissolved "In a flask equipped with a Galciumchloridrohr the solution was kept at 20 ⁰ G in motion while 0.03 g of boron trifluoride etherate were added, and then the stirring at that was Temperature continued for 3 hours. After the polymerization, the contents were prediluted with chloroform, and the diluted solution was poured into a large volume of ethanol containing a small volume of ammonia with vigorous stirring.

- 25 109829/1602

A white polymer was then obtained. The cured "was 0.97 Si <3- ^e -" viscosity was ^ y] = 0.483 dl / g (TI-II ?; 30 ⁰ C)

The IR spectrum of the 4-vinylphenyl (sinnamates showed by the OHo = CH-Eest (styrene type) caused absorptions in

C.

-1

close to 905 and 990 cm "" and one through -CE = OH- (trans) absorption caused near 975 cm =, in the IR spectrum of cationic polymerization products, the absorption near 905 and 990 cm had completely disappeared, and the

-1>

Absorption near 975 cm remains, and the absorption strength was of the same size as that in dementia speaking monomers was observed.

Example. 28 : -

4-Vinylphenylcinnama.t vrur.de polymerized under the same conditions as in Example 27, with. Except that the amount of trifluoroboron converted into the itherate was 0.01 g. The yield was 0.95 g with; a viscosity of / "? / 7 = 0.521 dl / g (TIIB ¹ ; 30 ⁰ C)

Example 29 : ...-- ■ ..

1.00 g of 4-Vinylphenylcinnamat was dissolved in 8.90 g Hsthylenchlorid "The solution was polymerized at -10 ⁰ C 21st After the treatment of Example 27, the polymer was isolated. The yield was 0.84 g with a viscosity of [lj] "0.592 dl / g (THE, 30 ⁰ C).

The polymer thus obtained was dissolved in chloroform. When converting this solution into a film on a glass plate at a distance of 15 cm from a high pressure mercury lamp (100 W) was placed as the light source and exposed to this light for 8 minutes, it became complete

- 26 -

109829/1602

SAD

Solution that

■ made insoluble. If a / by mixing the polymer made with about 4 wt% 5-nitroacenaphthene was formed into a film in a dark place and the same spaced at the same distance When exposed to a mercury lamp for 1.5 minutes, it was made insoluble. The same film also became insoluble made when exposed to an indoor light for 30 minutes.

Example 30 ?

1.00 2 ^ ^ -Tiiiylpheiiyl -iiitrocinnamat wurde- in 3 »00 g Hethylenchlcrid dissolved The solution was -Seamlessly under Süliron at 0 ⁰ C with 0.03 g Bcrtrifluoridätherat and 2.5 h the polymerization," allowed to proceed, the polymer was isolated by the same method as used in Example 27. The yield was 1.00 g with a viscosity of dl / g (03-IF; 30 ^° C.).

When producing a ο film from the polymer obtained according to the Ilethode of Example 27 and its Exposure to a mercury lamp made the film * completely insoluble.

Example 31 s

1.00 g ^/ + -Vinylphonyl-3-nitx- ⁱ ocinnamat was dissolved in 6.00 g ITitromethan. This solution was combined with 0.03 g of boron trifluoride etherate with stirring at 15 ^° C., the polymerization proceeded immediately, and the polymer formed in this way separated itself off as a sediment. The polymer was as applied according to the same Iiethode in Example 27, isolated with the rapid expansion was 1.00 g with a viscosity of = 0.250 dl / g (SLIF; 30 ⁰ C).

- 27 -

109829/1002

Example 3.2 :

1.00 g of 4-vinylphenyl - ^ - cyanocinnainate was dissolved in a mixture of 50,000 g of methylene chloride with 2.00 g of nitrobenzene. The solution was combined with 0.02 g of boron trifluoride etherate while stirring at -20 ° C. and allowed to polymerize for 3 h. The polymer was isolated by the same method as given in Example 27. Since this process involved the use of nitrobenzene, the entire operation was carried out in the dark. The yield was 0.90 g with a viscosity of [jj = 0.468 dl / g (TKO ¹ ; 30 ⁰ C).

h When a polymer was produced from this film and when the film was exposed in exactly the same way as in Example 27, the film was made completely insoluble ο

Example 53 s

0.62 g of 3-vinylphenyl cinnamate was dissolved in 1.90 g of litromethane. The solution was ^{combined with 0.01 g of boron trifluoride etherate at 18 °} C. while stirring and the polymerization was allowed to proceed for 4 hours. The polymer was isolated by the same method as used in Example 27. The yield was 0.52 g with a viscosity of III] = 0.053 dl / g (THF; 30 ^° C.).

When producing a film from the polymer obtained and then exposure to light in completely the same manner as in Example 29, the film became completely insoluble made.

Example 34;

1.00 g of 2-vinylphenylciniiamate was added in a mixture of 2.00 g Methylene chloride - dissolved with 1.00 g of nitromethaii. The solution

- 28-

109829/1602

BATH ORIGINAL

was combined with stirring at 18 ⁰ C with boron trifluoride etherate and 0.03 S allowed to proceed the polymerization then 4- Ii "The polymer was isolated by the same method as in Example 27 'The yield was 0.91 S ¹ ^" k Siller viscosity of IyJ = .0.152 'U / g (TBT ?; 30 ⁰ G).

Example 55 :

1.00 g of 4-isopropenylphenylciniiamate was dissolved in 3) 00 g of methylene chloride. The solution was combined with stirring at 20 ⁰ C with 0.01 g Bortrifluoridätiierat and then allowed ablaiifen polymerization during 23 h. The polymer was isolated by the same method as in Example 27. The yield was 0.44 g with a viscosity of / ⁷ JJ | = 0.03s dl / g (TKB ¹ ; 30 ⁰ O).

The polymer obtained was dissolved in chloroform and formed into an IPiIm on a glass plate. When the film dom exposed to light in the same manner as in Example 29 if the fiin was made insoluble.

Example 36 :

1.00 sec of 4-Iaopropenylphenylcinnaate was dissolved in 19.00 g of methylone chloride. The solution was combined with stirring at -25 ⁰ O with 0.03 g Boiirifluoridätherat and allowed to proceed for 23 h the polymerization. The polymer would be isolated by the same method as used in Example 27. The yield was 0.19 g with a viscosity of TiI = 0.068 dl / g (TIIF; 30 ⁰ O).

B.-Is-piöl 37:

1.00 fj 4-Vinylphouylciiinamat and 0.40 g Isobutylvinylätlier "were dissolved in 4.20 g Iluthylenchlorid. The solution was uator stirring at 0 ⁰ O with 0.03 g Bortrifluoridäthürat before agrees

- 29 -

109829/1802

and the polymerization 3 & allowed to proceed. The copolymer was used by the same method as in Example 27, isolated. The yield was 1.04 g with a viscosity of

^ J 50- ⁰ C). _v

Example 5 , 8 ;

1.00 g of 4-vinylplienyl-3-nitrocinnaniate and 0.33 g of isobutyl vinyl ether were dissolved in 4.00 g of methylene chloride. The solution was combined under Rühren'bei 0 ⁰ O with 0.03 g Bortrifluoriöütherat and the polymerization allowed to h.ablaufen 3. The copolymer! Sat vairde. by the same method as used in Example 27, isolated. The yield was 1.07 g with a viscosity of LJf =. 0.231 dl / g (THI; 30 ⁰ O),

Example 39;

1.00 g of 4-yynylphenyl cinnamate and 0.01 g of azobisiaobutyronitrile were dissolved in 2.00 g of tetrahydrofuran (TInT). This solution was polymerized in a vacuum sealed tube at 70 C 5.1 h _o The contents of the tube wur.de then poured under vigorous stirring into a large volume of ethanol. cause the isolation of the copolymer zti. The yield was 0.39 g with a viscosity of [> j] = 0.207 dl / g (THI ?; 30 ⁰ C).

Example 4-0 :

A solution of the same composition as. In Example 39, polymerization was carried out at 70 ° C. for 3 hours using the same procedure. The copolymer! Sat was by the same method as used in Example 39, isolated, The yield was 0.25 g with a viscosity of [TSS '= 0.093 dl / g (QHFy 30 ⁰ C).

A film was produced from the copolymer according to the procedure of Example 29 and exposed to light. As a result inxrdo the film made insoluble.

- 30 -

109828 / 160a bathroom original

2062526

Example 41 :

In 2.80 g tetrahydrofuran 1.00 g of 4-Vinylpheiiylcinnamat ₉ g ethyl acrylate 0.40 "and 0.014 g of azobisisobutyronitrile were dissolved. This solution was polymerized in a valruunab ge seals en tube at 70 ⁰ C for 35 aiii. The copolymer! Sat was isolated by the same method as used in Example 38. The yield was 0.24 g with a viscosity of ""? /./

= 0.110 dl / g CHEF; 30 ⁰ C).
Example 42 :

In 2.40 g tetrahydrofuran 1.00 g Ziratsüure-p-vinylplienyläster were 0.21 g of acrylonitrile and 0.012 g AaobisisobutyM "* ·" dissolved nitrile This solution vmrde in a voJiuumabgedichteton tube 80 min at 70 ⁰ C polymerized. The copolymer vmrde by the same method as used in Example 38, isolated "The yield was 0.29 g with a viscosity of ϊηΐ = 0.120 dl / g (LOW; 30 ⁰ C).

Example 43 ?

A bottle, protected from moisture and equipped with a calcium chloride tube, was loaded with a solution of 1.10 g of 4-Viij.ylphoiiyl-ß-styryl acrylate in 10.00 g of methylene chloride. The batch was mixed with 0.03 g of Bortririuci'idlllih ^ i'fit without ^{stirring at 25 0 O.} Continued at the same temperature for 3 h I vmrde the keep moving. After the polymerization, the contents were poured into a large volume of ethanol, which contained a small volume of ammonia, with vigorous stirring. In this way a white polymer was obtained. The yield was 1.08 g with a viscosity of " 0.444 dl / g CTHi ¹ J 30 ⁰ C).

Example 44:

g of 3-vinylphenyl-ß-styryl acrylate were in 10.00 g of methylene

- 31 -

109829/1602

BATH ORIGINAL

2062628

dissolved chloride. The solution was combined with 0.03 g of boron trifluoride etherate at 5 ° C. while stirring. Stirring was continued at the same temperature for 3.5 hours. Following the procedure of Example 43 below, the polymer was isolated. The yield was 1,02.g having a viscosity of yyyy = 0.129 dl / g (THF; 30 ⁰ C).

Example 45 :

A solution of 1.00 g of 2-vinylphenyl-ß-styryl in 10.00 g of methylene chloride was .vereinigt under stirring at 10 ⁰ C with 0.03 g of boron trifluoride etherate and then gpLassen 15h the polymerization to proceed. Following the procedure of Example W 44, the polymer was isolated. The yield was 0.39 g with a viscosity of / JJJ = 0.07 dl / g (THF; 30 ⁰ C).

Example 46 :

The polymerization was carried out under the same conditions as used in Example 43, except that 4-vinylphenyl-β-styryl acrylate was used in an amount of 1.00 g and boron trifluoride etherate in an amount of 0.01 g, respectively became. The yield was 0.96 g with a viscosity of jjjj = 0.491 dl / g (THFj 30 ⁰ C).

“The resulting polymer was dissolved in chloroform. When the solution has been formed into a film on a glass plate, which was arranged at a distance of 15 cm from a xenon lamp (500 W) as a light source and exposed to the light for 5 minutes, the film had been rendered completely insoluble.

Example 47 :

A solution of 0.8 g of 4-vinylphenyl-β-styryl acrylate and 0.02 g of isobutyl vinyl ether in 2.0 g of methylene chloride was added with stirring combined at -5 C with 0.003 g of boron trifluoride etherate and then

- 32 -

109829/1802

5 Ii allowed to polymerize. Following the procedure of Example ^ the copolymer was isolated. The yield was 0.49 g with a viscosity of Ίβ = 0.219 dl / g (THF; 30 ⁰ C).

Example 48 ;

A solution of 1.00 g of 4-yinylphenyl- ^ -cyano-ß-styryl acrylate in 10.00 g of methylene chloride was combined with 0.03 g of boron trifluoride etherate while stirring. Following the procedure of Example 43, the polymer was isolated. The yield was 0.84 g with a Yiskosüät of L 7 / J = 0.300 dl / g (THB ¹ ; 30 ⁰ C).

The polymer thus obtained was dissolved in chloroform. When this solution is spread on a glass plate and becomes a A film of uniform thickness was formed and then exposed to light by the same method used in Example 46 was made, the film was made insoluble.

Example 49 ;

0.99 g of 2-vinylphenyl- ■% cyano-β-styryl acrylate were dissolved in a mixture of 10.00 g of methylene chloride with 10.00 g of nitromethane. The solution was combined with 0.03 g of boron trifluoride etherate at 10 ° C. while stirring, and the polymerization was then allowed to proceed for 15 hours. When the same aftertreatment was carried out as in Example 43, the polymer was isolated. The yield was 0.86 g with a “viscosity of / = 0.138 dl / g (THF; 30 ^° C.).

Example 50 ;

A solution of 1.36 g of 4-isopropenyl-phenyl-ß-styryl in 20 g of methylene chloride were combined with stirring at 10 ⁰ C with 0.03 g of boron trifluoride etherate and the polymerization for 40 h

- 33 109829/1602

subjected. By carrying out the treatment in the same manner as in Example 4-3, the polymer was obtained. The yield was 0.77 g with a viscosity of L'Vl "0,114- dl / g (THP} 30 ⁰ C).

Example 51 »

A solution of 1.00 g of 4-vinylphenyl-ß-styryl, and 0.01 g of azobisisobutyronitrile in 2.00 g of dioxane was polymerized in a vacuum sealed tube 7 & at 60 ⁰ C. The contents were then poured into a large volume of ethanol with vigorous stirring to enable the polymer to be isolated. The yield was 0.34 g with a viscosity of Εηΐ = °> ¹ ° 5 dl / g (THFj 30 ⁰ G).

When a PiIm is made and lighted by the same method, was exposed as applied in Example 4-6, the film made insoluble.

Example 52 ;

A solution of 1.00 g of 2-vinylphenyl-ß-styryl, 0.38 g of ethyl acrylate and 0,014- g of azobisisobutyronitrile in 3.0 g of tetrahydrofuran was polymerized in a vacuum sealed tube for 90 min at 70 ⁰ C. The copolymer was isolated by the same method as used in Example 51. The yield was 0.19 g with a viscosity of fy] = 0.095 dl / g. (TKB ¹ J 30 ⁰ O). '

Example 53 ?

In one protected against moisture bottle, which was equipped with a Galciumchloridrohr, a solution of 1.04 to 5 g ß-Vinyloxyäthylcinnamat in 10 ml of toluene at -78 ⁰ G was cooled and, while maintaining at this temperature in movement, with 0.021 g boron trifluoride etherate combined.

- 34-109829/1602

At the same temperature, the agitation was continued for 2 hours. After the polymerization, the contents of the bottle were diluted with toluene and poured into a large volume of methanol which contained a small volume of ammonia to obtain a white polymer. The yield was 0,934- g and the reduced viscosity (1.07 g / dl) was 0.678 (THF; 30 ⁰ C).

The IR spectrum of ß-vinyloxyethyl cinnamate showed _{near absorptions due to the GH 0} = OH-Eestes (p-vinyloxyalkylrest)

—1 - 1

820 cm and 960 cm and an absorption due to the -CH = GH- (trans) residue close to 975 cm, while the absorptions close

-1 -1
820 cm and 960 cm were completely invisible, and the

_ ^]
Absorption near 975 cm in the IR spectrum of the products of the cationic polymerization remained. In addition, the absorption was of the same intensity as that of the monomer.

The polymer thus obtained was dissolved in benzene. The solution was formed into a film on a glass plate and 8 minutes with a high pressure mercury lamp (100 W) in a Was arranged a distance of 15 cm, exposed. Consequently the film was made completely insoluble. If a by combining the polymer with about 3 wt .-% 5-Hitroacenaphthen and picramid formed a film in the dark and exposed to the mercury lamp for 1.5 min the film was likewise rendered insoluble.

Example 54- ?

1.09 g of β-vinyloxyethyl cinnamate and 0.50 g of isobutyl vinyl ether ■ were dissolved in 14.0 g of toluene. This solution was cooled to -78 ⁰ C and combined under stirring with 0.03 g of boron trifluoride etherate. At the same temperature, the agitation was continued for 1 hour . The contents of the bottle became the

- 35 -

109829/1602

subjected to the same aftertreatment as in Example 53 to obtain a white copolymer. The yield was 1.57 g _} and the reduced viscosity (1.07 g / dL) was 1.8 μ.

The polymer was dissolved with benzene and formed into a film. When this film is 8 minutes after the mercury lamp When subjected to the same method as used in Example 53, the film was rendered completely insoluble. ■

Example 55?

A solution of 1.10 g of ß-Vinyloxyäthylcinnamat, 1.00 g styrene and 0.02 g of benzoyl peroxide in 4.00 g of benzene was / iinem vacuum-sealed tube 3 * 5 polymerized k ^ ei 70 ⁰ C. Thereafter, the contents of the tube were treated by the method of Example 53 to obtain a copolymer. The yield was 0.14 g and the reduced viscosity (1.05 g / dl) was 0.156.

Example 56 :

A mixture of 1.00 g of ß-Vinyloxyäthyl-3-methylcinnamate in 9.00 g of toluene was cooled to -78 ⁰ C and combined under stirring with 0.01 g BortrifÄioridätherat. At the same temperature, the agitation was continued for 2 hours. The contents were subjected to the same post-treatment as used in Example 53 to obtain a white polymer. The yield was 0.95 g and the reduced viscosity (1.05 g / dl) was 0.593.

The polymer was dissolved in tetrahydrofuran and formed into a film. When this film 6 min the mercury lamp by the same method used in Example 53, the film was rendered completely insoluble.

- 36 -

109829/1602

Example 57 ?

A solution of 1.00 g of ß-vinyloxyethyl-OC-cyanocinnamate in 9 »00 g of toluene was cooled to -40 ° 0 and, while it was kept moving, combined with 0.02 g of boron trifluoride etherate. At this temperature it became keeping moving Continued for 30 min. The polymer was by adding excess methanol, which contained ammonia, to the Content isolated. The yield was 0.97 g

Example 58 ?

A mixture of 1.00 g of ß-Vinyloxyäthyl-ß-styryl in 9j00 g of toluene was cooled to -40 ⁰ O, and, while being kept in motion, combined with 0.02 g of boron trifluoride etherate. At the same temperature, the agitation was continued for 3 hours. The contents were subjected to the same post-treatment as used in Example 53 to obtain a white polymer. The yield was 0.99 g of ₅ and the reduced viscosity (1.15 g / dL) was 0.412.

The polymer was dissolved in benzene, the solution was formed into a film on a glass plate and the mercury lamp Exposed for 6 minutes according to the method of Example 53. As a result, the film was made completely insoluble.

Example 59 ?

A solution of 1.22 g of ß-Vinyloxyäthyl-ß-styryl, and 0.50 g of isobutyl vinyl ether in 13.00 g toluene was cooled to -45 ⁰ and G combined with stirring with 0.034 g of boron trifluoride etherate. The keeping in motion was then carried out for 3 hours at the same temperature. The contents were subjected to the same post-treatment as used in Example 53 to obtain a white copolymer. The yield was 1.70 g, and the reduced

- 37 -109829/1602

The delicate viscosity (1.0 µg / dL) was 1.00. Example 60;

In one protected against moisture bottle, which was equipped with a calcium chloride tube, a solution of 1.00 g of 4- (ß - vinyl oxy) cooled -äthoxybenzylidenacetophenon in 9.00 g of methylene chloride at -25 ⁰ and G, ^wa / ^re was kept moving, combined with 0.020 g of boron trifluoride etherate. Keeping in motion was continued for 3.5 hours at the same temperature. After the polymerization, the contents were poured into a large volume of methanol containing a small volume of ammonia to give a light yellow poly. to receive merisat. The yield was 0.76 g and the reduced viscosity (0.5 g / dl) was 0.15 »

The polymer thus obtained was dissolved in a mixture of methyl ethyl ketone dissolved with chloroform. The solution was formed into a film on a glass plate and the high pressure mercury lamp (50 W) as a light source, which was placed at a distance of 15 cm, exposed. As a result, the movie became made insoluble »

Example 61;

A solution of 0.20 g of 4- (ß-Vinyloxy) -äthQxybenzylidenaceto-P phenone and 1.80 g of isobutyl vinyl ether in 2.00 g of methylene chloride was at room temperature (15 ° 0) with 0.9 mg of aluminum sulfate-sulfuric acid complex / Al ₂ (SO ^^ / 3H ₂ SG ₂ JZVH ₂ Oj. Stirring was continued for 3 "5 hours". After the polymerization, the contents were subjected to the same treatment as used in Example 60 to produce a light yellowish-brown polymer. The yield was 1.73 g, and the reduced viscosity was 0.55 x

The polymer obtained in this way was formed into a film and exposed to the mercury lamp for 10 minutes by the same method as in FIG

- 38 -

Example 60 applied, exposed. As a result, the Film made insoluble.

Example 62 :

A mixture of 1.00 g of 4- (ß-vinyloxy) ~ äthoxybenzylidenacetophenon, 0.50 g of styrene and 0.015 g of benzoyl peroxide in 3.00 g of dioxane was charged into a vacuum sealed glass tube and heated continuously for 6 hours at 70 ⁰ C. After the polymerization, the contents were subjected to the same treatment as used in Example 60 to obtain a polymer. The yield was 0.28 g and the reduced viscosity was 0.16.

A film formed from the polymer was exposed to light in the manner of Example 61. As a result, the Film made insoluble.

Example 63 :

A solution of 1.00 g ^z t -'- (ß-Yinyloxy) ätho3: ybenzylidenacetophenon in OO 9 ₅ g of methylene chloride was cooled to -37 ⁰ O and combined with 0.02 g of boron trifluoride etherate. At the same temperature, the agitation was continued for 3 hours. After the polymerization, the contents were subjected to the same post-treatment as used in Example 60 to obtain a light yellow polymerizate. The yield was 0.82 g and the reduced viscosity was 0.23 x

According to the same method used in Example 60, the polymer obtained in this way was shaped into a film and exposed to light. As a result, the film was made insoluble.

- 39 -

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Example 64 :

A solution of 1.00 g of 4 ^l - (ß ~ vinyloxy) -äthoxyberizylidenacetophenon and 0.50 g of isobutyl vinyl ether in 18.00 g of methylene chloride was cooled to -35 ⁰ C and combined with 0.03 g of boron trifluoride etherate. Stirring was continued for 2 hours at the same temperature. After the polymerization, the contents were treated in the same manner as in Example 60 to obtain a practically white polymerizate. The yield was 1.83 6 ^"un & ^ ^e reduced viscosity was 0.13 ·

The polymer thus obtained was formed into a film and exposed to light in the manner of Example 61. Consequently the film was made insoluble.

Example 65 ?

A solution of 0.50 g of 4 '- (β-vinyloxy) ethoxybenzylidene acetophenone and 4.50 g of isobutyl vinyl ether in 500 g of methylene chloride was combined with 2 mg of aluminum sulfate-sulfuric acid complex and kept ^{in motion at 15 to 16 °} C. for 20 hours held. After the polymerization, the contents were subjected to the same treatment as used in Example 60 to obtain a light yellowish brown polymerizate. The yield was 4.13 g and the reduced viscosity was 0.60.

A film formed from the resulting polymer was with Exposed to light in the manner of Example 61. As a result, the film was made insoluble.

Example 66 :

A solution of 1.00 g of 4- (ß-vinyloxy) -ethoxy-3-methoxybenzylidene acetophenone in 9.00 g of methylene chloride xvurde to -JO ⁰ C from-

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cooled and combined with 0.01 g of boron trifluoride etherate. At the same temperature, the 3 Ii agitation was continued. After the polymerization, the contents were treated in the same manner as in Example 60 to obtain a polymer. The yield was 0.85 g> and the reduced viscosity was 0.09.

Example 67 ?

A mixture of 1.50 g of 4- (ß-vinyloxy) -ethoxy-4-methylbenzylidenacetophenon in 14.00 g of methylene chloride was cooled to -30 ⁰ C and combined with 0.04 g of tin (IV) chloride. At the same temperature, the hold in motion was carried out for 3 hours. continued. Wax of the polymerization, the content was treated in the manner of Example 60, to obtain a slightly yellow (polymer. The yield was 1.27 g, and the reduced viscosity was 0.17 ·

The polymer thus obtained was formed into a film and exposed to light in the same manner as in Example 60. As a result, the film was made insoluble.

Example 68 ;

A mixture of 1.00 g of 4 '- (ß-vinyloxy) -äthoxyphenylbutadienalacetophenon in 9.00 g of methylene chloride was cooled to -25 ⁰ C and combined with 0.03 g of boron trifluoride etherate. At the same temperature, agitation was continued for 3 hours. After the polymerization, the contents were treated in the same manner as in Example 60 to obtain a polymer. The yield was 0.75 gj and the reduced viscosity was 0.18.

The polymer thus obtained was formed into ¹ µm and exposed to light in the manner of Example 60. The I ¹ Hm was made insoluble as a result.

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Claims (4)

Claims before 1. Process for the production of optically crosslinkable polymer, characterized in that one by the compound represented by the following formula; GH OR wherein R ^ represents the following radicals; OCOO »CH -f» OH = GH - 0-4- ■ Z GH CH, > _- co -4- oh »gh - ^ - ( _χ JS or OH »OH -J-—. GO-Xx and R _{n represents} -H or an alkenyl radical, and where η is an integer between 0 and 3 inclusive, m is an integer between 2 and 4 inclusive, Z is any substituent that is inactive with respect to phenolic hydroxyl radical and carboxylic acid chlorides and X is a sensitizing substituent, in the presence or absence of a polymerization catalyst with itself or with a chain polymerization - 42 - polymerized monomers. 2. The method according to claim 1, characterized in that that one, two or more kinds of cationic polymerization catalysts and radical polymerization catalysts can be used as catalyzation polymerisers. 3. The method according to claim 1, characterized net that GE by implementing one of the 3Por mel IUX reproduced connection, where IU ■ £ GH ₂ or -OOG "GH · £ OH" OH Y ^a and X is a halogen radical and η is an integer between 0 and 3 inclusive, m one integer between 2 and 4 inclusive, Z is any other than phenolic hydroxyl radical and carboxylic acid chlorides inactive substituent and Y is a sensitizing substituent and a compound represented by the following formula: R ₄ V wherein R _{4 represents} one of the following radicals: _r GH - GH, OCO = OH ■ £ GH = OH Y 109829/1602 CH ₂ - ^ j- O-CH = CH ₂ -CO -f CH β CH - ^ (ν ^ or ™ and -. '. ■ W is OH, LiO, ITaO or KO and η is an integer between 0 and J inclusive, m is one integer between 2 and 4 including, Z any, to phenolic hydroxyl radical and carboxylic acid chlorides inactive substituent and Y is a sensitizing substituent are, in the absence of a catalyst or in the presence of a basic catalyst, a mixture , ...>. .,. or quaternary of tertiary amine and quaternary ammonium salt ι ammonium salt is produced. 4. Optically crosslinkable polymer which, within the structure, has a given by the following equation Chain has; ■ f CHo-CRo ·> where R. is one of the following radicals! 109829/1602 OCOO - OH ⁷ H W -O -4 OH ₂ - ^ - 0000 m CH -4- CH r. OH -Cf- OH ₂ 00 4 OH «OH or -0 4 OH ~ OH and ■ R _{2 represents} -H or an alkenyl radical and η is an integer between 0 and 3 inclusive, m is an integer between 2 and 4 inclusive, Z is any other phenolic hydroxyl radical and carboxylic acid chlorides inactive substituent and X are a sensitizing substituent. 1Ο8 · ΐΙ / 16Ο2 ORIGINAL INSPECTED