DE2163525A1 - Process for the production of resins which are soluble in organic solvents and have a softening point which can be adjusted to a predetermined value - Google Patents

Description

"Process for the preparation of in organic solvents soluble resins with softening point adjustable to a predetermined value "

Priority: 23 December 1970 / Japan, registration no. 115 982/70

The present invention relates to a process for the production of harses which are soluble in organic solvents softening point adjustable to a predetermined value.

Resins which are soluble in an organic solvent and have a softening point which can be adjusted to a predetermined value are very desirable for a wide variety of applications, for example as paints, printing inks, adhesives, ₉ sizing agents for paper and additives for Kautschuk® Aue des ¹ US Pat. No. 2,689,231 is preparing a procedure "sur tltrmiieiifsu, 2? s»

2098 29/09 61

tion of a mixture of cyclopentadiene or dicyclopentadiene
and a reactive vinyl group-containing monomer in the absence of a solvent and in the absence of a catalyst. However, the polymer obtainable in this way from, for example, dicyclopentadiene and styrene has
a softening point in the range from 199 to 201 ⁰ C and
can therefore only be used to a limited extent. Also, the U.So Patent 3,468,837 relates to a process for preparing a resin having a softening point in the range 170-200 ⁰ C by means of thermal polymerization Pcl3 ^r a to Sicyclopentadien
enriched fission fraction of a petroleum, where oc-pinene has been added to the polymerization batch. By means of this
However, the process cannot regulate the value for the softening point of the polymer in the desired manner.
It is possible, by means of a further method, to regulate the softening point to a certain extent, with one
Mixture of cyclopentadiene or dicyclopentadiene with a
unsaturated aromatic hydrocarbon, such as styrene, in

Polymerized in the presence of a Friedel-Crafts catalyst

themselves
will. On an industrial scale, however, this procedure cannot be used because of the costs involved, especially since the use of a catalyst also necessitates an additional work-up stage in which the catalyst is removed from the polymer after the reaction has ended. If in such a polymerization in the presence of a
Friedel-Crafts catalyst cyclopentadiene is used in high concentrations, moreover forms a gel-like substance during the polymerization reaction, which in the reaction

209829/0951

tion product "remains suspended" and thus the yield is reduced. In addition, the resins obtainable in this way have a relative low softening point and, moreover, they lose their stability in the air and form after prolonged exposure to Air substances insoluble in organic solventsΌ

In spite of the favorable properties, such as sufficiently high oxidation stability and a degree of unsaturation suitable for practical purposes compared to the polymers produced in the presence of Friedel-Crafts catalysts, the only thermal polymerisation of cyclopentadienes and unsaturated aromatic hydrocarbons such as styrene, been available resins \ insufficiently used in practice, in particular because of their extremely high softening point _o

It should be noted that such resins for use in paints should, for example, have a softening point in the range from 130 to 160 ° so that they can also be used in combination with drying oils. • the person concerned should, however, have the resins have a softening point in the range of 80 to 100 ⁰ C for the application on the adhesive area. For paper sizes turn resins are highly desirable with a softening point of 50 to 6O ⁰ C. Although there is sufficient demand for resins with an adjustable value for the softening point, it has not hitherto been possible to regulate the softening point in the desired manner or to adjust the softening point accordingly.

2 0 9 f ·? ? / 0 9 5 1

to reduce accordingly.

The object of the invention is to remedy the above-mentioned disadvantages and difficulties and _r to provide a method available which allows to synthesize resins having a predetermined value for the softening point, and thus to provide products which, depending on the amount of the softening point as Paints, printing inks, adhesives, sizing agents ^ for paper and additives for the rubber industry can be used ο This object is achieved by the invention.

The inventive method for the preparation of organic solvent-soluble resins with adjustable to a predetermined value softening point is characterized in that cyclopentadiene, methyl cyclopentadiene and / or derived Diels-Alder oligomers in the absence of a catalyst at temperatures in the range of 200 to 35O ⁰ C is thermally polymerized together with at least one unsaturated aromatic hydrocarbon in the presence of controlled amounts of an inert hydrocarbon solvent which dissolves all monomeric reaction components.

In one of the starting components used according to the invention So it is cyclopentadiene, dicyclopentadiene, tricyclopentadiene, Tetraeyclopentadiene and other Diels-Alder ™ oligomers, in each case an end product with the desired Properties is obtained ο

2093 2 9/0951

The "starting substances in question do not need a high degree of purity have, and it can be used, for example, concentrated fractions that in thermal dimerization a C, fraction arise, this C, fraction as a by-product is obtained from the thermal decomposition of naphtha and corresponding petroleum fractions. With such a dimerization the cyclopentadiene or methylcyclopentadiene contained in such a fraction is converted into dicyclopentadiene, dimethylcyclopentadiene, a dimer of cyclopentadiene and methylcyclopentadiene, a dimer of cyclopentadiene and isoprene, a dimer converted from cyclopentadiene-piperylene and other corresponding dimeric substances »Most of the rest Components in this C ^ fraction, such as O ^ olefins,

C _c paraffins and other constituents are then made from ο ι

the fraction in question distilled off "

In the process according to the invention, at least one unsaturated aromatic hydrocarbon is used as the second reaction component, for example styrene, alkylated styrene derivatives such as α- or β-methylstyrene, α- ₉ m- and / or p-vinyltoluene, loaded and its alirylated derivatives or one fraction, which at dsr Zersetsung obtained a Irdölfraktion and the © romatlachen Yerbindungsn above containing such a Pyrelyssbefesnälu-ag @ u'at 2M / orf © n fraction contains üblicherv / eiss n <sh (3iA. ä ^ m bstroffenden saturated aromatischön Kolilamwasaerstoffea aiiok mooii ® see connections, wele-a © isa lahiien ä®T li? flmäi?, iag as 1jöstoi§q

> \ η "■.«% η, η? f _r λ; <ο

L ύ ίί ύ ί -3 / "J 4 -ä ί

form will be explained in more detail below «

The reaction mixture to be implemented according to the invention preferably has a monomer content in the range from 10 "to 95 percent by weight, while the remainder consists of the solvent in question. It is also particularly useful when this monomer mixture from 5 to 95 percent by weight from the unsaturated aromatic hydrocarbon and from 95 to 5 percent by weight composed of the cyclopentadiene component.

In the method, any hydrocarbon can be used as inert solvents are used, which is capable of the mixture of cyclopentadiene, methyl cyclopentadiene odez ^*: Diels-Alder Oligoraeren these compounds and from the respective unsaturated aromatic hydrocarbon, such as to dissolve styrene. Aromatic hydrocarbons such as benzene, toluene and xylenes are suitable for this purpose. Aliphatic hydrocarbons can also be used, such as hexane, isooctane, white spirit and other petroleum products such as solvent benzene and kerosene. By adding these solvent components, the softening point of the resins prepared according to the invention is adjusted to the desired value, the value for the softening point being ßo lower lies, the greater the amount of solvent used.

The reaction temperature is an essential file the method according to the invention. It must immediately be

- "- 203829 / 0Si-I-., ■

range from 200 "to 35O ⁰ C and is preferably in the range from 250 to 28O ⁰ C. Only within the temperature range given above can resins be produced which are soluble in organic solvents and in which the value for the softening point is set to a predetermined value Numerical value can be set ο If a reaction ^{temperature below 200 0} C is used, a gel forms and the resin in question is partially insoluble in the solvent in question. At a reaction temperature above 35O ⁰ C, on the other hand, there is a tendency to form black carbon-containing substances, because the resin in question decomposes at least in part at such high temperatures.

According to the invention, the implementation is usually within carried out a period of 10 minutes to 20 hours, wherein the actually required time to a certain extent also of the reaction temperature depends on. When using longer reaction times resins are generally obtained with a higher softening point, while extremely short reaction times lead to the polymer in question in part is insoluble and infusible because the reaction is terminated at too early a stage. Accordingly, the invention should The reaction should preferably be carried out until any amount of insoluble substance has completely disappeared is. The resin is used following the polymerization reaction obtained by removing excess solvent component and unreacted monomeric constituents © by vacuum distillation, or steam distillation as a heating element

209829 / 03S1

mixture separates β

As a result of the used in the process according to the invention At relatively high temperatures, the reaction is preferably carried out in a pressure-tight reactor with a pressure gauge and a thermometer. If appropriate, stirring can be carried out during the reaction. The inventive The process can be carried out either batchwise or continuously. According to a preferred embodiment an inert gas atmosphere is maintained in the reaction vessel for example from nitrogen or carbon dioxide.

Resins of the type indicated with a value for the softening point in the range from about 40 to 195 ^° C. can be produced in a very simple manner by means of the process according to the invention.

If, for a given ratio of monomeric cyclopentadiene or methylcyclopentadiene or oligomers derived therefrom, one adds As the amount of solvent increases as the unsaturated aromatic hydrocarbon increases, it is possible to keep the resin composition constant lower the softening point. Since the softening point of the polymer depends only on the ratio of the solvent depends on the monomer mixture used, the aromatic content of the resin - regardless of the desired softening point - set and in this way end products can be obtained that are suitable for the most diverse Applications are suitable.

209829/0 951

The method according to the invention accordingly offers the possibility of adjusting the aromatic content of the resin and the softening point of the same independently of one another produce the most varied of softening points, for example with softening points of 58 ⁰ C, 80 ⁰ C, 10 6 ° C, 130 ⁰ C and 155 ⁰ C.

In the process according to the invention, the softening point of the resins in question can be adjusted in a simple manner according to the following general equation t

■ 0? _m = A + B (T - 250) -

In this equation means

T = the softening point of the resin formed in C T = ⁰ adjustable in the range of 200 to 35O ⁰ C selected reaction temperature
ßi 7 = the proportion of unsaturated aromatic component

in the monomer mixture, expressed in mol / liter - the concentration of solvent in the reaction

system, expressed in moles / liter A, B, C and D are corresponding constants.

If you use the inventive method with a resin want to produce a certain softening point, a preliminary test can be carried out under freely chosen conditions, in order to get in this way the value for the above given

209829/0951

Determine constants A, B, G and D. The reaction conditions, namely T, / KJ and / ßj /, can then be chosen so that the resin with the desired softening point is formed in the subsequent actual polymerization reaction.

If, for example, dicyclopentadiene with styrene using a xylene mixture available on the market as a solvent is polymerized, bo these constants have approximately the following values s

A = approx. 180

B = approx. 1.0

C = about 10.0

D = approx. 14.0

According to another embodiment, however, it is also possible Resins with the most varied ratios of cyclopentadiene to unsaturated aromatic compound with one to produce a solid softening point of, for example 90 ° C, the relevant monomer ratios values of 3: 2, 7 r 3, 1: 1, 3: 7 or 2; 8 can accept.

The above embodiments are of particular practical importance because it has hitherto been an established fact it was considered that hydrocarbon resins of the type under consideration here with a given ratio of monomers cannot show any variation in the softening point.

The inventive method has, inter alia, the following

209829 / 09St.

the advantages of:

1) This process can be used to produce resins which are suitable for a wide variety of applications because the mixing ratio of the two different types of starting monomers can be adjusted so that the resin composition obtained by the method to the desired one Purpose corresponds, while on the other hand, the softening point is set in the desired manner regardless of this composition can be.

; 2) The softening point of the resin obtained can be determined extremely light and within a large area vary.

3) Virtually colorless resins can be produced which are readily soluble in hydrocarbon solvents, for example in benzene, toluene, xylene, benzene and in hydrocarbon solvents with a boiling range of up to 3 ^ 0 C and an aniline point of about 72 ⁰ Co Produce resins which can be mixed with drying or semi-drying oils in any ratio, for example with linseed oil, soybean oil and sunflower oil, and which can be modified in a simple manner by heating with these drying oils.

4-) It can be by means of the inventive method Resins with different levels of unsaturation accordingly produce a bromine number in the range from 30 to 120,

* 2 09829/0951

which calibration significantly facilitates the modification option with the addition of maleic anhydride "Accordingly can be such resins much better for a variety of applications to adapt, for example for paints ₉ inks for paper, adhesives and rubber mixtures, as the resins with high softening point, at the previously known methods can be obtained <>

5) Resins are obtained by means of the process according to the invention which have an extraordinary resistance to oxidation, which show no change even when left in the air for more than 1 month and only ^{show limited oxidation at a temperature of 200 °} C. and long-term exposure to air . However, these resins do not show any signs of decomposition under oxidizing conditions, as usually occur when using coating agents. If desired, however, resins which are to be used under particularly harsh conditions can also be admixed with customary antioxidants, for example 2,6-di-tert-butylphenol.

The examples illustrate the invention.

example 1

^ cyclopentadiene, hereinafter abbreviated as DCPD, styrene, and a commercially available mixture of xylenes! technical quality are reacted for 3 hours at a temperature of 260 to 265 ⁰ C in a stirrer-equipped autoclave of. After completion

209 8 29/0951

After the reaction, the autoclave is cooled and the reaction mixture is cooled to remove unreacted monomers Components and excess solvent distilled under reduced pressure. That way you get what you want Resin. In Table I below, the properties of resins are given when the concentration of the solvent is varied in the range from 10 to 90 percent by weight, while the monomer ratio of DCPD j styrene is constant at one Value of 70:30 is held »

Table I.

Ver
search
No. Solution
middle-
focus
tration,
Weight H Properties of the polymer ,. ^ **)
Colour / _{Bromine- #iHt} N
number ' Solubility'
in benzene 1
2
3
4th
5 90
70
50.
30th
10 Softening
point (O ₀ ) *) 5
5
. 6th
6th
6 ⁺ 80
76
64
68
66 soluble
1"
It
Il
I! 58
80
106
130
155 ♦) Determined according to the Japanese industrial.
JIS-K-2531-60
**) Colorimetrically on a sample of 2 g in 25 cm 'benzene
determined in accordance with A8TM-D-1544-58 T according to the Gardner scale.
* · *) Determined according to ASTM-D-H58.

209 8 29/0951

ORIGINAL INSPECTED

-H-

The numerical values in Table I confirm that with a reduction the concentration of the solvent but constant weight ratio of DCPD: styrene corresponding to 70:30. Resins with increasing softening point are obtained by this the desired regulation of the softening point through the addition of solvent according to the teaching of the invention made clear.

The resins given in Table I are soluble in benzene, toluene, xylene and in a hydrocarbon ^{solvent with a boiling range of 270 to 310 0} C and an aniline point of about. 72 ⁰ C and also in solvent benzene, and they can be mixed with linseed oil or soybean oil to in coating materials that are easy to use in practice can be overcooked. In addition, for example, the resin from experiment no. 4 can be added by adding maleic anhydride

i ·

be converted into a resin which has polar groups and a high softening point and is therefore particularly good good as a paint and printing ink.

If one, however, the reaction is performed as described above with the exclusion of the solvent, a resin having a softening point of more than 200 ⁰ O is obtained, which does not ätidert even when modifying the reaction conditions. If, on the other hand, the starting material from Experiment No. is allowed to ^{react for 25 hours at a temperature of 180 °} C., a gel-like product is obtained, of which only a very small amount is soluble in benzene.

209829/0961. _{0R | GlNAL INSP} cted

Example 2

DCPD, a mixture of o-, m- and p-vinyltoluene and toluene technical grade as a solvent are for 3 hours in an autoclave equipped with a stirrer at one temperature of 270 Ms 275 ° C, and then the reaction mixture is polymerized according to the procedure of Example 1 to obtain of the resin product worked up. In Table II are the properties of the resins thus obtained using the different solvent concentrations but at a constant one Weight ratio of DCPD to vinyl toluene of 70:30 indicated.

Table II

Ver
search
No. Solution
middle-
focus
tration,
Gew.jS Properties of the polymer colour bromine
number solubility
in benzene 6th
7th
8th I.
OOOI
VO <* CVJ I Softening
point (Oq) 3
4 "
5 70
70
68 soluble
η
η 85
112
135

The numerical values in Table II confirm that the softening point can be adjusted in the desired manner even when toluene is used as the solvent. The resins of experiments No. 6 to 8 are in benzene, toluene, xylene, a hydrocarbon solvent with a boiling range from 270 to 31O ⁰ C and

2-09829 / 0951. ·

an aniline point of 72 ⁰ C as well as soluble in solvent benzene, and they can be mixed in any ratio with linseed oil or soybean oil and can be boiled with these to form a coating agent. In addition, the herge-- Sun 'presented resins in any ratio with phenol resins miscible -

Example 3

A Cg fraction with a boiling range from 140 to 200 ⁰ C,. | Which was obtained from a pyrolyzed oil, which falls off as a by-product in the steam cracking of naphtha, and DCPD are thermally polymerized for 3 hours in an autoclave equipped with a stirrer at a temperature of 260 to 265 ° C, and the reaction mixture is then according to the Procedure of Example 1 with Recovery of Polymer Resins Worked Up In Table III below, the properties of the resins thus obtained are compiled, the weight ratio of DCPD to the Cq fraction having been varied.

209 3 29 / Ü9 51

Table III

Ver
search
No. DCPD
Concentrate
tration
Weight $ Properties of the polymer colour bromine
number solubility
in benzene 9
10
11
12th
13th
5 10
30th
50
70
80 Awakening
point / ο-, χ
ν W 7th
6 ⁺
6th
5
5 75
75
■ 73
73
72 soluble
Il
11
Il
Il 75
103
127
156
170

., The numerical values in Table III confirm that the expansion point of the resins in question varies as a function of the amount of the Cq fraction which simultaneously contains solvent components. The at test Nos. 9 "to 13 obtained resins are benzene, toluene, xylene, and a hydrocarbon solvent with a boiling range from 270 to 31o ⁰ C and an aniline point of about 72 ⁰ C alkalines also they are soluble in solvent naphtha and can be mixed with linseed oil or soybean oil, whereby coating agents are obtained when cooked with these oils.

Example 4

The CV fraction of pyrolysis oil, which is obtained in the steam columns of naphtha is heated 4- hours at 10O ⁰ C. Anechlieeeendee distilling gives a high boiling point

209829/0951.

Residue consisting of 88 percent by weight of dieyclopentadiene, 1.2 percent by weight of dimeric methylcyelopentadiene, 9 »5 percent by weight of a dimer of cyclopentadiene and isoprene or piperylene and 2.3 percent by weight of the CV fraction. This residue is used together with styrene and a commercially available xylene mixture of technical quality heated for 3 hours in an autoclave at 270 to 275 ° C. The reaction mixture is then treated according to the procedure of Example 1 to obtain the desired resins ·

- ■

i s _}

Table IV shows the properties of resins which are obtained at a constant weight ratio of high-boiling residue to styrene of 50:50 but with varying solvent concentrations ^:

■ ι ■ Table IV

Ver
search
No. Solution
middle-
focus
tration,
Weight # Properties of the polymer colour bromine
number solubility
in benzene U
15th
16 50
30th
10 Softening
point / O ₀ ν 4th
4th
4th 65
68
65 soluble
N
W. 85
109
135

The resins of experiments No. 14 to 16 are in benzene, toluene, xylene, a hydrocarbon solvent old with a boiling range of 270 to 310 ⁰ O and an aniline point of about 72 ⁰ C so-

20982 9/0951

as soluble in solvent benzene .. If you look at the corresponding polymerization reaction with a starting material of the same high cyclopentadiene content but in the presence of a Friedel-Craft -Catalyst carries out, then it is impossible to adequately to obtain only weakly colored resin products which are soluble in benzene. This example therefore confirms the advantages of the inventive method, after which the softening point can then also be adjusted in the desired manner, if such a reactive starting material as cyclopentadiene is used becomes β

Example 5

_; Methylcyclopentadiene, styrene and solvent benzene are thermally polymerized for 3 hours in an autoclave equipped with a stirrer at a temperature of 265 ° to 270 ° C. The reaction mixture is then worked up in accordance with the procedure of Example 1 to obtain the resin products. Table V below shows the properties of the methylcyclopentadiene au styrene of at a constant weight ratio

70:30 but obtained with varying solvent concentrations Resins listed.

209329/0951

Table V

Ver
-such
No. solution
middle
concentrate
tration,
Where? S Properties of the polymer colour Bronv
number solubility
in benzene 17th
18th
19th 50
30th
10 Softening
point / Op N 5
5 ⁺
5 72
70
68 soluble
Il
Il 110
124
145

The resins of tests Nos. 17 to 19 are soluble in benzene, toluene, xylene, ^1, a hydrocarbon solvent with a boiling range of 270-310 ⁰ C and an aniline point of about 72 ⁰ C and in solution benzene

Example 6

Cyclopentadiene, styrene and isooctane to 2 hours in an autoclave at a temperature of 270 to '280 C ⁰ polymerized c The thus-obtained reaction mixture is further worked up according to the procedure of Example. 1

In Table VI below are the properties of the so at a constant weight ratio of cyclopentadiene to 50:50 styrene but varying solvent concentrations that vary in the range from 20 to 60 percent by weight, obtained resins compiled.

0 ^ 29/0951

Table VI

Ver
search
No ο Solution
middle-
focus
tration,
Weight # Properties of the polymer colour Bromine-
.number solubility
in benzene 20th
21
22nd 60
40
20th Softening
point / Oq N 4th
4th
3 * 67
65
65 soluble
η
II 86
■ 100
125

The resins of experiments Rr. 20 to 22 are in benzene, toluene, xylene, a hydrocarbon solvent with a boiling point. range from 270 to 310 ⁰ C and an aniline point of about 72 ⁰ G as well as soluble in solvent benzene. In addition, they are mutually miscible with linseed oil and sunflower oil and can be boiled with these oils to form a coating agent ο

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Claims (4)

Claims Process for the preparation of resins which are soluble in organic solvents and which can be set to a predetermined value Softening point, characterized that cyclopentadiene, methylcyclopentadiene and / or derived therefrom; Diels-Alder oligomers in the absence of a catalyst at temperatures in the range from 200 to 350 ° C. together with at least one unsaturated aromatic hydrocarbon in the presence of controlled amounts of an inert hydrocarbon solvent which contains all monomeric reaction components dissolves, is thermally polymerized. 2. The method according to claim 1, characterized in that the Polymerization in the temperature range from 250 to 280 ° C is carried out. - · 3 «Method according to claim 1 and 2, characterized in that styrene, methyls tyr oil and / or vinyl toluene is used as the aromatic reaction component. 4. The method according to claim 1 to 3 »characterized in that the reaction mixture to be reacted has a monomer content in the range from 10 to 95 percent by weight«, 5 · Procedure according to. Claim 1 to 4, characterized in that that the reaction mixture to be reacted is 5 to 95 percent by weight from the unsaturated aromatic hydrocarbon, 209 8 2 9/0 951 based on the total amount of monomeric components, contains. 6c method according to claim 1 to 5, characterized in that that as an inert hydrocarbon solvent, benzene, Toluene, xylene, hexane, isooctane, white spirit and / or solvent benzene is used » 7 »Method according to claims 1 to 6, characterized in that that excess solvent and unreacted. monomeric components after the end of the polymerization Vacuum distillation or steam distillation are separated from the reaction mixture. 8 «Method according to claim 1 to 7> characterized in that resin components with a softening point in the range from 40 to 195 ⁰ C are produced. 209829/0951 ORIGINAL INSPECTED