JPH07238160A - Modifier for polymer - Google Patents

Abstract

PURPOSE:To obtain a modifier which can give a hydrophilic property to a copolymer copolymerized with it by reacting polyoxyalkylenepropenyl phenyl ether with a sulfating agent or a phosphating agent. CONSTITUTION:Allylphenol or isopropenylphenol and an alkylene oxide are subjected to an addition reaction under high-temperature and high-pressure conditions in the presence of an alkali catalyst to obtain a polyoxyalkylene propenyl phenyl ether. This product is reacted with a sulfating agent or a phosphating agent to obtain a modifier comprising a compound of formula I [wherein R<1> is H or methyl; R<2> is 1-propeny or isopropenyl; A is 2-4C alkylene; n is 1-100; X is -SO3M or a group of formula II or III; and M is H, an alkali (alkaline earth) metal atom, ammonium or an alkanolamine group]. When various monomers are copolymerized with 1-30wt.% this modifier in the presence of a polymerization initiator and a polymerization accelerator, the copolymers having a hydrophilic property can be obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer modifier, and more particularly, to a polymer modifier which is copolymerized with various monomers to impart hydrophilicity to the resulting polymer.

[0002]

2. Description of the Related Art Conventional polymer modifiers that impart hydrophilicity to polymers include, for example, monomer types such as sodium styrene sulfonate, sodium vinyl sulfonate, and hydroxyethyl acrylate. Examples include polyoxyethylene methacrylate, acrylic acid and acrylamide. These polymer modifiers are copolymerized with a hydrophobic monomer to introduce a polar group into the polymer for modification. Further, for the purpose of antistatic and antifogging, a surfactant such as sorbitan monooleate or polyoxyethylene lauryl ether is applied to or kneaded into the polymer to modify the polymer.

However, such conventional polymer modifiers do not always satisfy the required requirements, and their use and amount are limited.

[0004] For example, monomer type sodium styrenesulfonate, acrylamide, etc. are powdery and therefore difficult to handle in the copolymerization step, necessitating devising of manufacturing facilities, and thus not generally usable. Further, hydroxyethyl acrylate, polyoxyethylene methacrylate and the like are susceptible to hydrolysis due to the presence of a carboxylic acid ester group in the molecule, and it is difficult to use a polymer formed by copolymerization under strongly alkaline conditions. Further, the modification of antistatic property and antifogging property using a surfactant has problems in compatibility with a polymer and maintenance of long-term effect.

The object of the present invention is that it is easy to handle in a copolymerization step with a monomer and is widely used, and the polymer formed by copolymerization has antistatic property, antifogging property, compatibility, wettability and emulsion dispersion. The present invention is to provide a polymer modifier capable of improving the properties, film-forming properties and the like over a long period of time.

[0006]

The present invention provides a polymer modifier comprising a compound represented by the following general formula (I).

[0007]

[Chemical 2]

A in the above general formula is an alkylene group having 2 to 4 carbon atoms, for example, ethylene, propylene, butylene, isobutylene and the like. From the viewpoint of hydrophilicity, ethylene and propylene are preferable. (AO) _n and (OA) _n may be, for example, ethylene oxide (EO), propylene oxide (PO), butylene oxide or isobutylene oxide alone adduct, block adduct, random adduct, or a mixture thereof. . n is an integer of 1 to 100, and is preferably in the range of 1 to 50 from the viewpoint of physical properties given to the polymer. R ¹ is a hydrogen atom or a methyl group. R ² is a 1-propenyl group or an isopropenyl group. M is a hydrogen atom; an alkali metal atom such as sodium or potassium; calcium,
An alkaline earth metal atom such as magnesium; ammonium; an alkanolamine group such as monoethanolamine, triethanolamine, etc., and a mixed system thereof may be used.

The modifier of the present invention can be synthesized by employing a known method. For example, by adding alkylene oxide to allylphenol or isopropenylphenol under an alkaline catalyst at high temperature and high pressure, a polyoxyalkylenepropenylphenyl ether is obtained, to which a known sulfating agent or phosphorylating agent is added. The reaction can be carried out to obtain a sulfuric acid ester (salt) and a phosphoric acid ester (salt) (neutralizing with a basic substance if necessary). The phosphate ester (salt) is
It may be a mixture of a monoester (salt) and a diester (salt), and the ratio thereof is determined by the amount of water and the amount of phosphorylating agent contained in the reaction system of the phosphoric acid esterification reaction.

Since the polymer modifier of the present invention comprises a compound having a polymerizable propenyl group and a hydrophilic group, it is possible to modify the polymer produced by copolymerizing it with various monomers. it can.

The modifying agent of the present invention is intended to be modified by imparting a hydrophilic group to the polymer.
It modifies polymer physical properties such as antistatic property, antifogging property, compatibility, wettability, emulsion dispersibility and film forming property. The target polymer is not particularly limited and can be applied to various polymers such as water-insoluble, water-dispersible, and water-soluble.

For example, AB, which is a water-insoluble polymer
Regarding S resin, vinyl chloride resin and the like, by introducing a hydrophilic group into the inside or the surface of the polymer, the antistatic property and antifogging property of the polymer can be improved. Further, for acrylic resin fibers and the like, the dyeing property can be improved by introducing a hydrophilic group, and for SBR, the dispersibility of an inorganic filler such as calcium carbonate can be improved by introducing a hydrophilic group. Further, regarding the vinyl acetate emulsion, the film forming property can be improved by making the surface of the polymer particles hydrophilic.

Further, by introducing the modifier of the present invention into polyvinyl alcohol, which is a water-soluble polymer, it is possible to easily convert water-soluble polyvinyl alcohol into a water-soluble polymer, which has conventionally been troublesome to dissolve even with warm water. Can be improved to dissolve.

In order to modify a polymer using the polymer modifier of the present invention, a monomer as a raw material of each polymer may be copolymerized with the polymer modifier of the present invention. The polymerization method is not particularly limited, and can be selected from emulsion polymerization, suspension polymerization, solution polymerization and the like depending on the type and application of the target polymer.

The amount of the polymer modifier used in the present invention is 1 to 30% by weight, preferably 3 to 15% by weight, more preferably 5 to 10% by weight, based on all the monomers. If it is less than the above range, the effect used is insufficient, and if it exceeds the above range, physical properties of the polymer are deteriorated.

As the polymerization initiator, conventionally known ones can be used, and examples thereof include hydrogen peroxide, potassium persulfate, ammonium persulfate, t-butylperoxybivalate, azobisisobutyronitrile and benzoyl peroxide. Is mentioned. As the polymerization accelerator, sodium hydrogen sulfite, ferrous ammonium sulfate, etc. can be used.

The polymerization conditions such as the polymerization temperature and the polymerization time are not particularly limited, and can be appropriately set depending on the type of the target polymer and the application.

[0018]

EXAMPLES The present invention will be specifically described below with reference to examples. (%, Parts are based on weight.) Production Example 1 (Production of modifier [B]) In a reaction vessel equipped with a stirrer, a thermometer and a reflux tube, 94 g of phenol (1.0 mol) and 40 g of NaOH ( (1.0 mol) and 210 g of acetone were charged, and the internal temperature was raised to 40 ° C. with stirring. Next, allyl chloride 76.
5 g (1.0 mol) was added dropwise over 1 hour, and after the addition was completed, the reaction was carried out at 40 ° C. for 2 hours. Next, the reaction product was filtered to remove by-produced NaCl, and then acetone was removed under reduced pressure to obtain 130 g (yield 97.0%) of allyl phenyl ether.

67 g of this allyl phenyl ether (0.
(5 mol) was charged into an autoclave, and the mixture was held at 150 ° C. for 5 hours while stirring to carry out a rearrangement reaction to obtain allylphenol. Next, once cooled to room temperature, 1.4 g of NaOH was added as a catalyst, and the inside of the autoclave was replaced with N _2, and then 220 g (5.0) of ethylene oxide (EO) at 130 ° C. under a pressure of 1 to ² kg / cm ^2. 2- (1-propenyl) phenol E
287 g of an O-average 10-mol addition product was obtained. The allyl group is E
At the time of O addition reaction, it was changed to a 1-propenyl group.

Next, 287 g (0.5 mol) of this 2- (1-propenyl) phenol EO average 10 mol adduct.
Was charged into a reaction vessel equipped with a stirrer and a thermometer,
Charge 48.5 g (0.5 mol) of sulfamic acid, 1
The reaction was carried out at 30 ° C. for 2 hours, and the modifier of the present invention, 2-
There were obtained 335.5 g of a sulfuric acid ester ammonium salt of a 10-mol adduct of (1-propenyl) phenol EO.

Production Example 2 (Production of modifier [C]) In a reaction vessel equipped with a stirrer, a thermometer, and a reflux tube, 94 g (1.0 mol) of phenol, 40 g (1.0 mol) of NaOH and 210 g of acetone were added. Was charged, and the internal temperature was raised to 40 ° C. with stirring. Next, allyl chloride 76.
5 g (1.0 mol) was added dropwise over 1 hour, and after the addition was completed, the reaction was carried out at 40 ° C. for 2 hours. Next, the reaction product was filtered to remove by-produced NaCl, and then acetone was removed under reduced pressure to obtain 130 g (yield 97.0%) of allyl phenyl ether.

67 g of this allyl phenyl ether (0.
(5 mol) was charged into an autoclave, and the mixture was held at 150 ° C. for 5 hours while stirring to carry out a rearrangement reaction to obtain allylphenol. Next, once cooled to room temperature, 1.4 g of NaOH was added as a catalyst, and the inside of the autoclave was replaced with N _2, and then 220 g (5.0) of ethylene oxide (EO) at 130 ° C. under a pressure of 1 to ² kg / cm ^2. 2- (1-propenyl) phenol E
287 g of O10 mol adduct was obtained. The allyl group was changed to a 1-propenyl group during the EO addition reaction.

Next, 287 g (0.5 mol) of this 2- (1-propenyl) phenol EO 10 mol adduct was charged into a reaction vessel equipped with a stirrer and a thermometer, and the internal temperature was 70 ° C.
The temperature is raised to 24.1 g and phosphoric anhydride 24.1 g (0.1
7 mol) was added over 30 minutes. 70 ~ after completion of addition
The reaction was carried out at 75 ° C. for 7 hours, and the modifier of the present invention, 2-
311.1 g of phosphoric acid ester of (1-propenyl) phenol EO 10 mol adduct was obtained. The ratio (molar ratio) of the monoester and diester of this phosphoric acid ester was measured by NMR.
The result measured by (phosphorus) was monoester / diester = 60/40.

Production Example 3 (Production of modifier [D]) p-isopropenylphenol 134 was placed in an autoclave.
g (1.0 mol) and 48% KOH 3.0 as catalyst
After being charged with g and dehydrated under reduced pressure at 120 ° C., the inside of the autoclave was replaced with N ₂ . Next, ethylene oxide (E
O) 220 g (5.0 mol) was gradually added, and the addition reaction was carried out at 130 ° C. under a pressure of 1 to ² kg / cm ² to obtain 354 g of p-isopropenylphenol EO average 5 mol adduct. .

Next, 177 g (0.5 mol) of this p-isopropenylphenol EO average 5 mol adduct was charged into a reaction vessel equipped with a stirrer and a thermometer, and then 48.5 g of sulfamic acid (0. (5 mol) and charged at 130 ° C. for 2 hours to obtain 225.5 g of a sulfuric acid ester ammonium salt of a p-isopropenylphenol EO 5 mol adduct which is a modifier of the present invention.

Production Example 4 (Production of Modifier [I]) 67 g of p-isopropenylphenol was added to an autoclave.
(0.5 mol) and 0.6 g of 48% KOH as catalyst
Was charged and dehydrated under reduced pressure at 120 ° C., and then the inside of the autoclave was replaced with N ₂ . Next, 1-2 kg / c at 130 ° C
ethylene oxide (EO) 44 under a pressure of m ^2.
g (1.0 mol) was added to obtain 111 g of p-isopropenylphenol EO2 mol adduct.

Next, 111 g (0.5 mol) of this p-isopropenylphenol EO2 mol adduct was stirred with a stirrer and
A reaction vessel equipped with a thermometer was charged, the internal temperature was raised to 70 ° C., and 4.5 g (0.25 mol) of water was charged while stirring. Subsequently, 35.5 g (0.25 mol) of phosphoric anhydride was added over 30 minutes, and then the mixture was reacted at 70 to 75 ° C. for 7 hours to give 2 mol of p-isopropenylphenol EO, which is the modifier of the present invention. 151 g of phosphoric acid monoester of adduct
Got

Examples 1-5 and Comparative Example 1 In a 1000 ml autoclave, deionized water 450
g, partially saponified polyvinyl acetate (dispersant) 180 m
g, 300 g of vinyl chloride monomer, 75 mg of t-butyl peroxyvivalate, and Production Examples 1 to 3 as a modifier.
15 g of the modifiers [A] to [E] of the present invention (polyoxyethylene (n = 10) methacrylic acid ester in Comparative Example 1) represented by the following formula, which were produced in the same manner as in Example 4, were charged, and the mixture was heated to 58 ° C. For 5 hours. The vinyl chloride copolymer slurry thus produced was extracted, washed with water and dried to obtain a powdery copolymer.

A 0.2 mm-thick sheet was prepared from the copolymer of the powder using a hot roll and a hot press, and the surface resistivity and the contact angle were measured. Further, the same measurement was performed on the sheet after being immersed in a 5% NaOH aqueous solution for 24 hours. The results are shown in Table 1.

[0030]

[Chemical 3]

[0031]

[Chemical 4]

[0032]

[Table 1]

As is apparent from the table, the modifier of the present invention improved the antistatic property and surface hydrophilicity of the polymer.

Examples 6 to 10 and Comparative Example 2 3 parts of distilled water were placed in a reaction vessel equipped with a stirrer, a thermometer and a reflux tube.
00 g and partially saponified polyvinyl alcohol 8 g were charged and the temperature was raised to 70 ° C. to dissolve the partially saponified polyvinyl alcohol. Next, 0.3 g of ammonium persulfate was charged, followed by 200 g of vinyl acetate and Production Examples 1 to 1.
The modifiers [D] and [F] of the present invention produced in the same manner as
6 g of [I] (represented by the following formula) was added dropwise over 3 hours to carry out polymerization to obtain an emulsion.

The obtained emulsion was applied to a glass plate and left standing at 3 ° C. for 16 hours to evaluate the film forming property of the film. The results are shown in Table 2.

In Comparative Example 2, no modifier was used.

[0037]

[Chemical 5]

[0038]

[Table 2]

Examples 11 to 15 and Comparative Example 3 In a reaction vessel equipped with a stirrer, a thermometer, and a reflux tube, 100 g of toluene, 50 g of methyl methacrylate, 50 g of ethyl acrylate, and a modification of the present invention represented by the above chemical formula. 10 g of the modifying agents [J] to [L] of the present invention represented by the following formula, which are produced in the same manner as in the quality agents [D] and [E] and Production Examples 1 to 4.
And charged with 0.5 g of azobisisobutyronitrile,
Polymerization was carried out by heating at 80 ° C. for 5 hours. After completion of polymerization
Toluene was removed under reduced pressure to obtain a polymer.

10 g of this polymer was added to 100 ° C. hot water at 60 ° C.
The emulsion dispersion stability was evaluated after the addition to 100 g, stirring with a homodisper for 10 minutes, and cooling (after 3 hours). The results are shown in Table 3.

In Comparative Example 3, no modifier was used.

[0042]

[Chemical 6]

[0043]

[Table 3]

Examples 16 to 21 and Comparative Example 4 In a polymerization can, 2000 g of vinyl acetate and the type of modifier of the present invention shown in Table 4 ([A], [C], [D], and [I] are as described above. [M] is represented by the following formula), the amount (g), and 1500 g of methanol were added. Next, the temperature was raised while stirring the system under a nitrogen stream, and when the temperature reached 60 ° C., a solution of 2.0 g of azobisisobutyronitrile dissolved in 150 g of methyl alcohol was added to initiate polymerization. . The solid content concentration of the polymerization system was analyzed from the start of the polymerization, and the polymerization was terminated when the solid content concentration reached 50%. Methyl alcohol vapor was blown into this copolymer solution to remove unreacted vinyl acetate to obtain a methyl alcohol solution of the copolymer.

Next, the copolymer concentration of this copolymer solution was adjusted to 25% with methyl alcohol. This solution 100
When 0 g was kept at 40 ° C. and a hydrous methyl alcohol solution containing sodium hydroxide in an equimolar amount to the vinyl acetate unit was added with stirring, a saponified product was deposited and finally a gel was obtained. This gel was crushed, washed well with methyl alcohol, and then dried in an air stream at 80 ° C.
A VA-based copolymer was obtained.

A PVA polymer polymerized by the same procedure as above without using a modifier was used as a comparative sample (Comparative Example 4).

20 g of each of these PVA-based copolymer and PVA polymer was put into 500 g of water at 20 ° C., and the solubility was visually evaluated after stirring for 10 minutes with a magnetic stirrer. The results are shown in Table 4.

[0048]

[Chemical 7]

[0049]

[Table 4]

As is apparent from the table, the PVA-based copolymer obtained by copolymerizing the modifier of the present invention has improved solubility in low temperature water.

Examples 22 to 26 and Comparative Example 5 Polymerization was carried out by a known method using the raw materials (parts) shown in Table 5 (polymerization temperature 5 ° C., polymerization time 13 hours, conversion 60).
%) And solidified to obtain an SBR rubber (crumb rubber).

Next, to 100 parts of these SBR rubbers,
Sulfur 2.0 parts, zinc white 5.0 parts, stearic acid 1.0
Part, 1,3-diphenylguanidine (vulcanizing agent D) 0.5
Part, dibenzothiazyl disulfide (vulcanizing agent DM) 1.
5 parts, 100 parts of light calcium carbonate are blended, and 140
The rubber was vulcanized at 30 ° C. for 30 minutes and the rubber physical properties were measured. The results are shown in Table 5.

The modifiers [B], [G] of the present invention,
[I] and [M] are represented by the above chemical formulas. [N]
Is represented by the following formula.

[0054]

[Chemical 8]

[0055]

[Table 5]

As is apparent from the table, in Examples 22 to 26 using the modifier of the present invention, the physical properties of rubber are improved, and the effect of improving the dispersibility of the light calcium carbonate is shown. It is being appreciated.

[0057]

INDUSTRIAL APPLICABILITY The polymer modifier of the present invention is easy to handle in the copolymerization step with various monomers and is used widely. Polymers produced by copolymerization of the polymer modifier of the present invention and various monomers have improved antistatic properties, antifogging properties, compatibility, wettability, emulsion dispersibility, film-forming properties, etc. over a long period of time. To be done.

Claims (1)

[Claims] 1. A polymer modifier comprising a compound represented by the following general formula (I). [Chemical 1]