JPS5859202A - Production of low-molecular, unsaturated vinyl polymer - Google Patents

Abstract

PURPOSE:To obtain the titled, low-viscosity, high-activity polymer suitable for use in paints, etc., by reacting a low-molecular vinyl polymer terminated with a carboxyl or hydroxyl group with a polymerizable monomer having a functional group. CONSTITUTION:A carboxyl or hydroxyl group-terminated, low-molecular vinyl polymer, number-average MW of about 300-9,000, is synthesized by polymerizing a copolymerizable vinyl monomer (e.g., styrene) in the presence of a chain transfer agent which is a compound of formulaIor II, wherein R1 and R2 are each a 1-12C hydrocarbyl (e.g., 2-mercaptoethanol, thioglycolic acid). The purpose low-molecular, unsaturated vinyl polymer is obtained by reacting the above-produced polymer with a polymerizable monomer having a functional group which can be added to or condensed with the terminal groups (e.g., hydroxyethyl acrylate, methylolacrylamide).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is a low molecular unsaturated vinyl polymer, which is produced by producing a low molecular unsaturated vinyl polymer, and then introducing an unsaturated group using the terminal carboxyl i or the terminal hydroxyl group of i. There have been many proposals regarding the production of amorphous pinyl-based polymers, and the general method is to react with the functional group of the copolymerized gynomer. Another possible unsaturated functional group
An unsaturated vinylyl polymer is synthesized by adding f-. When obtaining a low-molecular unsaturated vinyl polymer using this method, it is generally done by adding an aliphatic mercaptan as a chain transfer agent to the base Vitel copolymer before introducing unsaturated groups. ing. However, with this method, when synthesizing a vinyl polymer with a small amount of functional groups, the probability is that a low-molecular base vinyl polymer may or may not have some functional groups.

is created. Therefore, it is not possible to introduce unsaturated groups into a low-molecular base vinyl polymer that does not have this functional group, so it is left as it is with ]I! Adhesive, Adhesive Tsuru Composition K
When combined with P, it does not participate in the crosslinking reaction, resulting in the disadvantage that the physical properties of the hard material are inferior.

Therefore, the inventors of the present invention have developed an unsaturated vinyl-based polymer with low molecular weight that has no drawbacks! As a result of extensive research in order to obtain a polyester resin, it was possible to synthesize the base vinyl polymer before introducing unsaturated groups.
When a specific mercaptan@ is used as a chain transfer agent, the base vinyl base 1 has a very high probability of having a carboxyl or hydroxyl functional group at least at the end of the molecule.
It was discovered that the desired low-molecular-weight unsaturated vinyl polymer can be obtained by reacting this polymer with an unsaturated ``alcoholic group'' monomer.
Thus, according to the present invention, (&) represents a hydrocarbon group of the following general formula (1) (% formula %) (RIIfiC1-12) as a chain transfer agent.

゛ Particularly suitable are AlΦ-lene group or r-IJ-lene group) or the following general formula (■) HB-R-COOH... (厘) (R2 is the above-mentioned R
Same as 1) One or two copolymerizable vinyl yarn monomers are uniformly polymerized in the presence of the compound shown in 1) to have a carboxyl group or a hydroxyl group at the molecular end and have a molecular weight of approximately several thousand! 10
Synthesize a low molecular weight vinyl polymer with a molecular weight of 0 to 9,000 (hereinafter referred to as "substrate vinyl polymer"), and then synthesize the terminal carboxyl group or terminal hydrogel of the substrate vinyl polymer. Provided is a method for producing a low-molecular-weight unsaturated vinyl polymer by reacting a polymerizable vinyl monomer having a functional group with addition reactivity or condensation reactivity with the base. Synthesis of the base vinyl polymer in each reaction step (Copolymerizable vinyl monomers used include styrene, a-methylstyrene,
Vinyl toluene, acrylic esters (methyl, ethyl, phthyl, 2-ethylhexyl, octyl, cyclohexyl esters), methacrylic esters (methyl,
ethyl.

Butyl: 2-ethylhexyl, lauryl, stearyl ester)% Acrylonitrile, metacyclonitrile, vinyl acetate, and long chain esters of acrylic acid and methacrylic acid (@Recording i) containing furkyl groups, polyester groups, etc. A vinyl monomer having monomer groups 1Pv with or without a functional group, -
1. For example, those shown in Table 2 below are copolymerized. Possibly a molecular weight a, but also a carboxyl group or a hydroxyl group 1
It is also possible to introduce fif.

Furthermore, in accordance with the present invention, representative examples of the compound represented by the general formula 0) are as follows.

2-Mercaptoethanol (R1=02H4)6-
Mercaptoethanol (R<:, OsTim)
4-Mercaptobutanol (“1: CaHe)
Typical examples of compounds with the general formula (seal) include thioglycol (R2: 0H2) thiosalcylic acid.
(R2:◎) etc.

On the other hand, compounds used as chain transfer agents in Chinese #'1
The use of mercaptans in (1) tFi is 0.3 to 5 niiri) excellent,
The weight range is preferably from 2 to 10%. The number of mercaptans used is 171. If the molecular weight is less than 3 times, there is a drawback that the molecular weight of the base vinyl polymer cannot be reduced.

On the other hand, if the use exceeds 30% ft4, the physical properties of hard materials will be confused.
turn into.

Copolymerization reaction 1j for obtaining base vinyl polymer f.

In addition to the above-mentioned components, a thermal polymerization initiator such as benzoyl peroxide, and a mixture of kevinyl-based heptamers,
4 Shigekura Yuu^ usually 6n~14rlU for 2 hours ~ 10F
Reacting during Wj is done by pressing the button. A carboxyl group- or hydroxyl group-containing vinyl monomer may be added to the monomer mixture from the beginning during the copolymerization reaction.

The base vinyl polymer obtained from Kagushi has a carboxyl group or a water-sensitive functional group at least at the end of the molecule. The low-molecular-weight unsaturated vinyl polymer of the invention is produced by: The introduction of the unsaturated group is carried out by reacting a carboxyl group or hydroxyl group in the base vinyl polymer with a vinyl heptadmer having a group capable of addition or condensation reaction by a generally known method. Typical examples of the vinyl nitrate 911 are shown in Tables 1 and 2 below.

Table 2 Low-molecular-weight unsaturated vinyl polymers obtained by combing and c
Town can.

The 11th section and the section that specifically indicate the favorite in the practical and comparative examples under the podium indicate the heavy section and the weight section.

Example 1 Add 100 parts of toluene to a reaction vessel and heat to 110°C with a force of 2
It was hot. Then a mixture of 2-mercaptoethanol 8iB methyl methacrylate 80 parts 2-hydrobodiethyl 7-acrylate 12 parts benzoyl peroxide 1 part was added dropwise to VC in toluene at 110°C over 3 hours, followed by 3 hours at 110°C.
A base vinyl polymer solution having a number average molecular weight of about 4,000 was obtained by aging for a period of time. Next, 70 parts of a 1:1 adduct of inphorone diisocyanate and 2- and droxyethyl methacrylate and 0.1 part of hydroquinone were added to the vinyl polymer solution.
The reaction was carried out at 110° C., and the end point of the reaction was defined as the point where the N00 value became 1N or less. The viscosity of the low-molecular-weight unsaturated vinyl polymer r4 solution obtained by removing toluene under reduced pressure was 80 points. This resin is coated with a film J
When UL 2ns was applied to a glass plate and irradiated with 2 megalabds (MR) using a scanning electron beam irradiation device, it hardened well, and the desired 77 tons extracted from the coating was 1
% or less.

Example 2 100 parts of toluene was added to a reaction vessel and heated to 110°C. Then, a mixture of thioglycolic acid 10@2-ethylhexyl acrylate 817111 methacrylic acid 9 parts and benzoyl peroxide 1 part was added dropwise to toluene at f1-1nn°C for 3 hours, and then at 110°C.
After aging for 6 hours, a base vinyl polymer solution (f) having a number average 6-7 weight of about 2000 was obtained. Next, add 14 parts of hegelicidyl methacrylate, 0.1 part of hydroquinone and 0.5 part of tributylamine to the VC# vinyl polymer solution,
The reaction was carried out at 0°C, and the point at which the acid value became 1 or less was defined as the end point of the reaction. Although toluene was removed under reduced pressure from the low molecular unsaturated vinyl thread polymer solution obtained in this way, the viscosity was 6 voids. 51 J*% of benzoin was added to this buffing fat, and when it was coated on a glass plate to a film thickness of 20 mm and irradiated with light from a distance of 20 m for 60 seconds using a high-pressure water lamp, it hardened well. The extractable content of the obtained membrane was less than 1%.

Comparative Example 1 Octyl mercaptan 10.162-
ethylhexyl acrylate) 72iftt methacrylic l121. Part a benzoyl peroxide.

Claims (1)

[Scope of Claims] (A) As a chain propagating agent, the following general formula (iris) H8-R1-
OH, -,00,(1) (R1#i (indicates a hydrocarbon base group of h ~ 12) or the following general formula (1) % formula % (1) (R2#i is the same as R1 above) One kind of vinyl monomer that can be copolymerized in the presence of a compound #f2 has a number average molecular weight of about 300 and has a carboxyl group or a hydroxyl group at the molecular end.
~9. Low-molecular unsaturation obtained by synthesizing a low-molecular-weight vinyl yarn polymer of nOO, and then (b) reacting the terminal carboxyl group or terminal hydroxyl group of the skeleton low-molecular-weight vinyl polymer with an addition-reactive or monomer. A method for producing a vinyl polymer.