JPS60112746A - Novel vinyl compound - Google Patents

Abstract

NEW MATERIAL:A vinyl compound of formula I (R is H or CH3). EXAMPLE:N-Cyclopropylacrylamide. USE:Useful as an adsorbent and light shielding material, etc. The polymer of the vinyl compound is a thermoplastic high polymer of the high-temperature hydrophobic type soluble in water within low temperature regions and insoluble in water within high temperature regions. The transition temperature of the aqueous solution thereof is <=45 deg.C. PREPARATION:As shown in the reaction formula, acryloyl chloride or methacryloyl chloride is reacted with triethylamine and cychlopropylamine in a solvent, e.g. benzene, acetone or toluene, and 0-10 deg.C to give the compound of formula I . The vinyl compound is soluble in water, methyl alcohol, ethyl alcohol, N,N-dimethylformamide, N,N-diethylformamide, acetone and dioxane, etc. and insoluble in n-hexane and n-heptane.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to vinyl compounds having N-cyclopropylacrylamide groups in ll'J 2i%.

The present inventors previously discovered that a polymer of N-isopropylacrylamide, N-isopropylmethacrylamide, N-n-propylacrylamide, or N-n-propylmethacrylamide is hydrophilic in a low temperature range below the transition temperature. They found that the aqueous solution is transparent, and when heated to a temperature higher than the transition temperature, it becomes hydrophobic and becomes opaque, and proposed that this quality be used to make a light-shielding material.

However, the above-mentioned polymers all have a transition temperature of 45° C. or lower in their aqueous solutions, which limits their range of use considerably.

The present inventors will develop materials with different transition temperatures and a wider range of applications (in the formula R
may be the same or different for each 111th position, and have the property of being insoluble at high temperatures.In other words, the inversion temperature of a 1% by weight aqueous solution of poly(toco-cyclopropylacrylamide) radically polymerized in the solution state is Although it depends on the polymerization conditions, the transition temperature of an aqueous solution of 11% poly(N-cyclopropylmethacrylamide) at 45 to 47°C is 57°C.
C to 60 C, and it was discovered that an aqueous solution of both copolymers has a transition temperature between 45 to 60 C depending on their composition ratio, and the present invention was completed based on this finding.

The vinyl compound of the present invention is a novel compound that has not been described in any literature, and is synthesized, for example, as follows.

(J CH-=CR+ (C,H-CH)*N-HCIV
Dragon O "H TenCH2GHz (R in the formula represents hydrogen or C1 (,) The solvent used here is limited to a solvent that does not react with CH2=CR-COC,e, and alcohols and amines are not allowed. However, there are no particular controls for other solvents, and GQ
Benzene, acetone, toluene, etc. are used. The reaction temperature varies depending on the type of solvent and other conditions, but is 10°C.
Less than is desirable.

At temperatures above 10°C, side reactions occur, making it difficult to produce vinyl compounds.

To isolate the target compound from the reaction mixture thus obtained, first remove triethylamine hydrochloride or cyclopropylamine hydrochloride by filtration, and then remove the solvent from the filtrate using a rotary evaporator. Then, it is distilled under reduced pressure. If the product is colored due to impurities mixed in during vacuum distillation, it can be purified by recrystallization to obtain a highly pure product. Target object g)-Cyclopropylacrylamide (84°C/1mmHg) + or N-cyclopropylmethacrylamide (102"C/I
TrlI! IHg) is a transparent liquid (crystallizes in a short time) whose rjAr point is N-cyclopropylacrylamide: 45°C5N-cyclopropylmethacrylamide: leap °C.

Regarding the melting properties of the vinyl compound of the present invention.

Water, methyl alcohol, ethyl alcohol, rXHN-
Dimethyl; 1; soluble in lumami, N, N-diethylformamide, dimethylsulfoxy, acetone, dio; 1-san, detrahydride, zoroloporum, carbon tetrachloride, etc., n-hegysan, Almost insoluble in n-heptane.

Since the vinyl compound of the present invention has a CH2=CR- group, it can be identified by IR, NMR, and mass spectroscopy.

The vinyl compound polymer of the present invention dissolves in water at low temperatures,
It is a high-jjat-jfl hydrated thermoreversible polymer that is insoluble in water at high temperatures. This polymer utilizes thermoplastic properties in the middle of the film, and uses a young absorbing agent, i. '
! ;: Can be used for T' surface l in many ways.

The present invention will now be explained in more detail by way of implementation and examples.

Fruit 11"j 19111 Put 363g of triethylamine, 200g of noclozolopylamine and 450ml of hibenzene into a 1e volume Erlenmeyer flask, cool with ice, bring the contents to the temperature of 10"C rice vinegar 21'A), and while stirring. , in which a mixed solution of 30 ml of acrylic acid chloride and 20 ml of benzene was added.
It was slowly dripped from the lower funnel over a period of about 3 hours.

After completion of the dropwise addition, the reaction solution was left to cool for a day and night, filtered, and benzene was removed from the filtrate using a rotary evaporator and concentrated. Then distilled under reduced pressure to a boiling point of 84"C/
A colorless and transparent fraction of 1 mm Hg was collected. This material crystallized immediately upon standing IIi.

By the above operation, a crystalline substance with a melting point of 45°C 29. Q g
I got it.

The elemental analysis value (as C6H9No) of this substance is as follows.

Actual measurements: 63.71 8.68 12.25 The mass spectrum of this substance is shown in Figure 1, the infrared absorption spectrum in Figure 2, and the NMR spectrum in Figure 3.

The results of these spectral analyzes are as follows.

Mass spectrometry 2 to 4+ = 111 1R analysis (K'Br): 1665 cy-' (C
H2=Cf()3290 crn' (-NH-) 1625σ-'(>C=O) NMR analysis: 0.45p4 (-CH of cyclopropyl group
2) 0,65p disorder (-CH2- of cyclopropyl group)
8,20p (-NH-1 2,50ppm (Impurity D?vl SO H)3
, 30 pr+11 (H of impurity H20) From the above analysis results, it was confirmed that this substance was N-cyclopropylacrylamide.

Example 2 Methacrylic acid chloride 3 instead of acrylic acid chloride
Except for using 6 ml, it was heated (same as Example 1, boiling point 102°/1 n+m Hg, melting point 60
℃, 32.6 g of a colorless and transparent crystalline substance was obtained.

The elemental analysis value (C7Hll No.) of this substance is as follows.

0 H(g) N(1) Calculated value 67.20 8.80 1120 Actual ill value
66.42 9.54 10.84The mass spectrum of this substance is shown in Figure 4, and the infrared absorption spectrum is shown in Figure 5.
The NMR spectrum is shown in FIG.

The results of these spectral analyzes are as follows.

Mass spectrometry: M” = 125 CH31R analysis (K
Br): 1658m' (CH2=C-)332
0(-m-' (-NH-) 1618 cm-'(>C=O) NMR analysis: 1.0OpIi1 (-CH2- of cyclopropyl group) 1.22p+ store (-C of cyclopropyl group
H2-) 7.9811 groups (-open-) 2.50 pln (Impurity DM SO) H) 3.30
(9) (H of impurity H20) From the results of the above two analyses, it was confirmed that this substance was N-cyclopropylmethacrylamide.

Reference Example 1 N-cyclopropylacrylamide obtained in Example 15.
17 g and 17.18 g of a benzene solution containing 1% azobisisobutyronitrile were placed in an ampoule, degassed under reduced pressure using liquid nitrogen, and the upper part was sealed with a burner. This ampoule was heated at a humidity of 75° C. for 6 minutes to carry out a polymerization reaction. At this time, as the polymerization reaction progressed, poly(N-cyclopropylacrylamide) was precipitated. After the polymerization reaction, the ampoule was opened and poured into benzene-n-hexane to dissolve unreacted monomers, and the insoluble portion was collected (
Yield -514.70g). The obtained polymer was made into a methanol solution, and the viscosity was measured using an Ubbelohde viscometer, and the intrinsic viscosity [η] was 2.20.

The obtained poly(N-cyclopropylacrylamide) was dissolved in water to prepare a 1% by weight aqueous solution, and this aqueous solution was heated using a spectrophotometer while increasing the temperature at a potato temperature rate of 1"C/min. The relationship between the transmittance in nm and temperature was determined, and the results are shown as a graph in FIG.

As is clear from this graph, poly(N-cyclopropylacrylamide) is dissolved in water at low temperatures, but begins to precipitate at 44°C, and the amount of precipitation rapidly increases as the temperature rises until 46°C. Then, the transmittance at 500 nm is 09
6, indicating that it is insoluble in water.

Reference Example 2 4.95 g of N-cyclopropylmethacrylamide obtained in Example 2 and 17.44 g of a benzene solution containing 1% azobisisobutyronitrile were placed in an ampoule, and degassed under reduced pressure using liquid nitrogen. , the top was sealed with a burner. This ampoule was heated at a temperature of 75"C for 1 hour to perform a polymerization reaction. At this time, poly (N-cyclopropyl methacrylamide) was precipitated along with the polymerization reaction. After the polymerization reaction,
The ampoule was opened and poured into benzene-n-hexane to dissolve - with unreacted monomers, and the insoluble portion was collected (yield: 3.16 g').

The obtained polymer was made into a methanol solution, and the viscosity was measured using an Ubbelohde viscometer, and the intrinsic viscosity [η] was 0.30.

The flaked poly(N-cyclopropylmethacrylamide) was dissolved in water to prepare a 1% by weight aqueous solution, and this aqueous solution was heated using a spectrophotometer at a temperature increase rate of 1 °C/I former n. The relationship between the transmittance at 500 nm and temperature was determined. The results are shown in FIG. 8 as a graph.

As is clear from this graph, poly(N-cyclopropylmethacrylamide) is dissolved in the low temperature range, but begins to precipitate at 59°C, and the amount of precipitation increases rapidly as the temperature rises to 111X. It can be seen that the transmittance at 500 nm is 0%, indicating that it is insoluble in water.

[Brief explanation of drawings]

FIG. 1 shows the mass spectrum of N-cyclopropylacrylamide, FIG. 2 shows the infrared absorption spectrum of N-cyclopropylacrylamide, and FIG. 3 shows the NMR spectrum of N-cyclopropylacrylamide. FIG. 4 shows the mass spectrum of N-cyclopropylmethacrylamide, FIG. 5 shows the infrared absorption spectrum of N-cyclopropylmethacrylamide, and FIG. 6 shows the NMR spectrum of N-cyclopropylmethacrylamide. No. 71-1 shows the relationship between temperature and light transmission/inclination at 500 nm for a 1% by weight aqueous solution of poly(N-cyclopropylacrylamide). FIG. 8 shows the button 17 (N-
The relationship between temperature and light transmittance at 5001 m for a 1% by weight aqueous solution of cyclopropylmethacrylamide is shown. 41 people with permission] 22 Engineering Director Kawa 1) Hirobe No.
! ,,' 4000 3000 2000 1600 12 demons) 0
8QOε+On. Wave Takeshi (OMj No. 6 Figure 420 PPM No. 7 [Z 0 20 40 60 80 ] 00 Wetness (C) No. B i, yj 1% ("c) Government Office Procedures Correction Book May 9, 1980 Commissioner of the Japan Patent Office Kazuo Wakasugi Patent Application No. 219006 of 1982 & Name of the invention: New vinyl compound & Relationship with the person making the amendment Patent applicant: 1-3-1 Kasumigaseki, Chiyoda-ku, Tokyo (114) Director of the Agency of Industrial Science and Technology Kawa 1) Hirobemoto Designated agent a Contents of amendment (1) “(o4-OH-)” in the second line of page 8 of the specification
J wor(>O-0) Correct to J. (2) Correct r(>0-0)J on the 4th line of page 8 of the specification to r(>(1-0)J). (4) Correct r(>(>) on line 12 of page 9 of the specification. 0-0) J to Ha ``(., - Corrected to Zen Itto.

Claims (1)

[Claims] (1) General formula %formula% (R in the formula represents hydrogen or CH3) A vinyl compound represented by