JPS58104911A - Reactive cyclized resin - Google Patents

Abstract

PURPOSE:A reactive cyclized resin, obtained by cyclizing a specific random copolymer of cetylene with a conjugated diene compound, having a reactivity, and suitable for many industrial purposes, and having diallyl active methylene groups. CONSTITUTION:A reactive cyclized resin obtained by cyclizing a random copolymer of acetylene with a conjugated diene compound having rich 1,4-bonds and 200-10,000, preferably 500-5,000, molecular weight in an organic solvent, e.g. benzene, in the presence of an acidic catalyst, e.g. chlorosulfonic acid, in an atmosphere of an inert gas, etc. at 50-250 deg.C under stirring for a given time, and removing the catalyst and solvent. The starting raw material is obtained by random copolymerizing acetylene with a conjugated diene compound, e.g. butadiene. USE:Printing, coating materials, adhesive, coating and electrical insulating materials.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is characterized in that it is rich in 1.4 bonds and has a molecular weight of 200 to 10.
000. The present invention relates to a reactive cyclized resin which is a cyclized reaction product of an acetylene-conjugated diene compound random copolymer preferably having a molecular weight of 500 to 5,000.

It has been known for a long time that when natural rubber or synthetic polybutadiene or polyisoprene rubber is treated with an acid catalyst such as concentrated sulfuric acid or tin tetrachloride, the double bond opens and a cyclized product is obtained as a polymer compound that generally has a cyclized structure. Are known. The properties of the cyclized product vary depending on the type of acid catalyst used, the amount used, reaction time, reaction temperature and other conditions.

In the cyclization reaction of high molecular weight compounds, increasing the polymer concentration increases the solution viscosity and makes it difficult to react due to the large molecular weight. It can only be carried out in concentration.

In JP-A-49-113892, when low molecular weight butadiene is used for cyclization of polybutadiene, the solution viscosity is low;
It is easy to handle even when the polymer concentration of the reaction solution is increased.
It is disclosed that gelation can be avoided even at a concentration of 20% or more.

These cyclized polymer compounds are all compounds made of hydrocarbons and have a certain amount of double bonds, so they are not reactive, and there is no possibility of chemical modification. Limited to the field.

The present inventors previously discovered that if acetylene and a conjugated diene compound are randomly copolymerized under specific conditions, a random copolymerization having viscosity or elasticity can be obtained, and a patent is currently being applied for (for example, 55-075227). The acetylene-conjugated diene random copolymer thus obtained is rich in 1°4 bonds and has diallyl type active methylene hydrogen due to acetylene-conjugated diene bonds.

-CH=CH-Cl2-CR=CR2- (where R and R2 are hydrogen, halogen, or C0-C6 hydrocarbon) Because of this active hydrogen, this acetylene-conjugated diene random copolymer is It has a much higher reactivity than diene homopolymer.

By subjecting this ace+:rene-conjugated diene copolymer to a cyclization reaction, the present inventors achieved high reactivity with diallyl-type active methylene hydrogen compared to the cyclization reaction product of conventional conjugated diene polymers. I learned that it is possible to obtain a cyclized resin with

The present invention is therefore rich in 1,4 bonds and has a molecular weight of 200 to 10,000. The present invention relates to a reactive cyclized resin which is a cyclized reaction product of an acetylene-conjugated diene compound random copolymer preferably having a molecular weight of 500 to 5,000.

The raw material acetylene-conjugated diene compound random copolymer is prepared by, for example, the method described in JP-A No. 55-075227, in which acetylene and the general CH= C-C-CH are prepared.
2 (wherein R and R2 are the same or different and each means hydrogen, halogen, or a C-C6 hydrocarbon group) by random copolymerization of conjugated diene compounds.

Conjugated diene compounds include butadiene, isop27
, ga. . Hm □' ,, 2.3-'; l ~ 2-.

Examples include:

The cyclized resin of the present invention can be produced by cyclizing the above copolymer using an acid catalyst in an organic solvent in a conventional manner. As acid catalysts, chlorosulfonic acid,
Inorganic acids such as perchloric acid; organic acids such as oxalic acid, benzenesulfonic acid, toluenesulfonic acid, or their halides; 7 Riedel-Crafts reagents such as boron trisulfide, aluminum chloride, tin tetrachloride, titanium tetrachloride, or Complexes such as the etherate can be used.

The amount used varies depending on the type of catalyst, reaction conditions, etc., but is generally 0.0
01 to 30 weight ratio is used.

The reaction mixture is stirred in an organic solvent such as habenzene, toluene, xylene, carbon tetrachloride, or chloroform at a temperature of 50 to 250 degrees for a predetermined period of time under an inert gas atmosphere or in a sealed container. After the reaction is completed, the catalyst can be removed by washing with water or the like and the solvent can be distilled off, or the product can be obtained by reprecipitation in a large amount of a non-solvent such as methanol.

It is also possible to add the reaction solution as it is into a non-solvent with vigorous stirring to perform reprecipitation and catalyst removal at the same time.

Accurate measurement of the cyclization rate in cyclized resins is difficult;
Although it is certainly possible to confirm the progress of the reaction using infrared spectroscopy, etc., it is difficult to quantify using this method. In general, in polymers having double bonds, the quantity of double bonds is determined by measuring the iodine value by addition of halogen, but this is also unreliable for cyclized resins.

Here, double bonds are measured using the NMI+ (nuclear magnetic resonance) spectrum measurement method, and the difference between the quantitative value of the raw material copolymer and the quantitative value of the produced cyclized product is considered to be the cyclization rate. , was used as a measure of the progress of the reaction.

The low molecular weight liquid reactive cyclized resins produced by this method are suitable for many industrial purposes.

They are suitable, for example, as softeners for rubber, for the production of films, coatings and moldings that can be cured by reticulation, and as self-drying oils or as additives to other drying oils. That is, the fields of application include printing, paints, adhesives, coatings, electrical edge materials, etc.

Compared to linear raw material resins, reactive cyclized resins contain compounds with unsaturated cyclic structures (cyclohexadiene,
cyclopentadiene), it can have high hardness when formed into a film.

This hardness can be freely controlled by changing the cyclization rate.

Next, the present invention will be described with reference to reference examples (manufacturing examples of acetylene-butadiene copolymers) and examples.

Reference Example 1 After purging a cylindrical glass reaction vessel of 51 with nitrogen, 30 mmol of nickel naphthenic acid and 2 parts of dry toluene were charged with 9 parts as a solvent, the amount of water in the system was measured, and deoxidized deionized water was added to this. is added in an amount such that the total water content is 150 mmol.

-Next, the temperature was raised to 20°C, and 210 mmol of Jetylua 1" Luminilamk Tetroid (in the form of a 4 mol/1 tolu hexane solution) was added under stirring, and immediately a mixed gas of acetylene/butadiene (molar ratio 1/10) was added. The reaction temperature is maintained at 30°C and the reaction is allowed to proceed for 6 hours. After the gas injection is completed, 100 d of deionized water is added to stop the reaction. The catalyst residue solvent is removed by a known method, and a slightly yellow A/ Copolymer B 1020.? is obtained.

Figure 1 shows that the produced copolymer is dissolved in deuterated chloroborum,
This is an NMR spectrum measured at room temperature at 100 MH2 using tetramethylsilane as an internal standard.

The peak at 2.1δ is assigned to the methylene hydrogen of butadiene in the butadiene-butadiene bond.

CH2-CH=CH-CH3-CH2-CH=CH-C
The H22,8δ peak is assigned to diallyl methylene hydrogen, that is, methylene hydrogen of butadiene when acetylene and butadiene are combined.

-CH=CH-di CH=CH-CH ``The color of the methylene hydrogen of butadiene bonded is 1.4 except for 5.5 δ,
It is assigned to the methylene hydrogen of 1 diacetylene. -CH2-Falling Tomoe-CH2- and -CH=CH- The acetylene content in this copolymer determined from the NMR spectrum was 9.1 mol%. Furthermore, as a result of measuring the microstructure of the double bond using the Morello method, we found that cis-1,4
88% bond, 6% trans-1°4 bond, and 1.2
The bond was 6i.

The measured number average molecular weight of G, P, C was 2200.

Reference Example 2 The synthesis method of Reference Example 1 was carried out using the same method and conditions except that a mixed gas of acetylene/butadiene (molar ratio: 3/IO) was introduced and the reaction time was 12 hours. Yellow-brown liquid polymer A/B copolymer 103
3! ? get.

The acetylene content in the copolymer determined by NMR spectrum was 2-3 mol%. Furthermore, the microstructure is cis-
There were 82% 1,4 bonds, 13% trans-1°4 bonds, and 5% 1,2 bonds.

The measured number average molecular weight of G, P, C was 1700.

Example 1 50y of acetylene-butadiene copolymer containing 9.1 mol% of acetylene obtained in Reference Example 1 and having a molecular weight of 2200, 501' of xylene; 5g of p-toluenesulfonic acid was added to 11
Place in a glass flask and incubate for 7 hours under nitrogen atmosphere.
Reflux at 5°C. Thereafter, the mixture is cooled to room temperature and dropped into methanol to precipitate the reaction product. The reprecipitation is repeated several times, and then the solvent is distilled off using a rotary evaporator to obtain a brown liquid reaction product.

FIG. 27 is an NMR spectrum of this reaction product.

The broad peak of 1 to 2 δ is assigned to methylene hydrogen in the cyclic structure. The peaks at 2°lδ, 2.8δ, and 5.5δ are the same as the structure of the raw material copolymer.

From this NMR spectrum, it was confirmed that this reactant was a reactive cyclized copolymer having a methylene group with a cyclic structure and a diallyl type active methylene group. The cyclization rate of this product was 40.4%.

Table 1 shows the relationship between the degree of cyclization and properties during production and time.

Table 1 Time dependence of cyclization reaction Example 2 Acetylene content obtained in Reference Example 2: 23 mol% 1 Molecular weight: 17
A reaction similar to Example 1 was carried out using the acetylene-butadiene copolymer No. 00. A brown liquid was obtained as a reaction product.

FIG. 3 is an NMR spectrum of this reaction product.

This confirmed that it was a reactive cyclized copolymer with a cyclization rate of 28.6%.

Table 2 shows the relationship between the degree of cyclization and properties during production and time.

Table 2 Time dependence of cyclization reaction Comparative example Molecular weight 2000. Polybutadiene containing 75% cis-1,4 bonds, 24% trans-1.4 bonds, and 1% l,2-bonds was reacted in the same manner as in Example 1.

As a result, a brown powder was obtained.

Figure 4 shows the NMR spectrum of this reaction product.

□ In this case, there are peaks assigned to cyclic methylene hydrogen at 1 to 2δ'', methylene hydrogen of l butadiene at 2.lδ, and methine hydrogen of butadiene at 5.46.

Example 3 Using the same reaction apparatus as in Example 1, a similar reaction was carried out using an acetylene-isoprene copolymer with an acetylene content of 16.7 mol % and a molecular weight of 1900 instead of the acetylene-butadiene copolymer. Ta. The same treatment as in Example 1 was performed to obtain a brown liquid. The nuclear magnetic resonance spectrum of this product has a sharp peak at 1.76 (methyl hydrogen of isoprene), a peak of methylene hydrogen of isoprene when bonding isoprene-isoprene at 2.1δ, 2.
The peak at 8δ is diallyl type methylene water L4, the small peak at δ is the methylene hydrogen of 3,4-bonded isoprene, the broad peak at 5.36 is lo, the methine hydrogen of 4-bonded isoprene, and the methine hydrogen of acetylene. A peak assigned to was obtained. Furthermore, a broad peak attributed to methylene hydrogen in a cyclic structure was obtained at 1 to 2 δ.

From this nuclear magnetic resonance spectrum, it was confirmed that this reactant was a reactive cyclized copolymer having a methylene group of a cyclic compound and a diallyl type active methylene group.

The cyclization rate of this product was 45%.

Example 4 Using the same reaction apparatus as in Example Section 1, a similar reaction was carried out using an acetylene-chloroprene copolymer with an acetylene content of 9.1 mol% and a molecular weight of 2400 instead of the acetylene-butadiene copolymer. Ta. A brown liquid was obtained as a product. In the nuclear magnetic resonance spectrum of this product, in addition to the peaks at 2.3[delta], 3.0[delta], and 5.4[delta] of the raw material coelectrode, there was a broad peak of 1 to 2[delta] attributable to methylene hydrogen in a cyclic structure. This confirmed that it was a reactive cyclized copolymer with a cyclization rate of 22%.

[Brief explanation of the drawing]

Figure 1 is the NMR spectrum of the acetylene-butadiene copolymer obtained in Reference Example 1, Figure 2 is the NMR spectrum of the reactive cyclized resin of the present invention obtained in Example 1, and Figure 3 is the NMR spectrum of the reactive cyclized resin of the present invention obtained in Example 1. The NMR spectrum of the reactive cyclized resin of the present invention obtained in Example 2, and FIG. 4 is the NMR spectrum of the polybutadiene cyclized reaction product obtained in Comparative Example.

Claims (2)

[Claims] (1) Rich in 1.4 bonds, molecular weight 200 to 10°0
A reactive cyclized resin having a diallyl type active methylene group, which is a cyclization reaction product of a 00 acetylene-conjugated diene compound random copolymer. (2) The reactive cyclized resin according to claim 1, which has a molecular weight of 500 to 5,000. (31) The reactive cyclized resin according to claim 1 or 2, wherein the conjugated diene compound is butadiene.