JPS62290708A - Durable epoxy (meth)acrylic polymer and its production - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION 3 DETAILED DESCRIPTION OF THE INVENTION Epoxy resins are widely used today for surface coatings, adhesives, castings, laminates and electronic component encapsulation purposes. Most of these epoxy resins are 2,2-bis(4
'-Hydroxyphenyl) furononine [bisphenol A] and shrimp chlorohydrin. This reaction produces a polymer having a main chain consisting of an ether bond between the bisphenol A structure and the hydroxypropylene moiety. ,-! There is also one epoxy group (oxirane) at each end of the polymer backbone. These resins can be cured by reacting their epoxy groups with crosslinking agents such as anhydrides, amines, and acids. When exfoliated, epoxides have good tensile strength, excellent electrical insulation properties, and excellent adhesion to many surfaces.

However, a major weakness of these conventional epoxy resins is their lack of outdoor durability. Ether bonds and aromatic rings in their main chains are responsible for poor stability against UV radiation and oxidation. These limitations prevent these epoxy resins from being used in systems requiring long-term outdoor exposure.

To date, two approaches have been taken to produce durable epoxides. One is low molecular weight cyclic or acrylic die? one related to the synthesis and use of glycidyl methacrylate (GMA);
Concerning the synthesis and use of copolymers. Both of these methods produce epoxides that are more durable than bisphenol A-based resins, but both have significant deficiencies.

Cyclic epoxides are not polymers, but simply have a very low molecular weight segment linking two epoxy groups. Such materials tend not to have the excellent physical properties of traditional epoxides.

In systems based on random copolymers of GMA, there is no controlled arrangement of epoxy groups, i.e., these copolymers have a random distribution of epoxy groups along the entire backbone of the methacrylate chain. . Bisphenol A
When an epoxy group is placed at the end of a polymer chain, as seen in epoxy resin, it imparts important properties such as toughness. Random placement of epoxy groups degrades the final properties.

Bisphenol Ai-based epoxides are well known and commercially available (e.g. 5hel
Epon resin from one company and DE from DOW
R epoxide series). Cyclic epoxides are also commercially available (eg, EFIL-4221 from Union Carbide, a cycloaliphatic diepoxide).

Methacrylate copolymers with randomly distributed OMA have been used in the paint industry (U.S. Pat. No. 3,8
17,946-17, Id. No. 4.027.066, Id. No. 3,730,930 and Id. No. 4.34 to No. 144), but GkAk' in the A segment.
jr: I cannot find a single patent or publication that reports on any ABA triblock methacrylate polymers.

Patents and publications related to GTP report that the process can be used to create block structures (
U.S. Patent No. 4,417,034, U.S. Patent No. 4.50 & 88
No. 0, No. 4,414,372, No. 4.524,1
No. 96 and No. 4.5. ! 14,724).

However, none of these disclose the epoxy triblock structure or the advantages of that structure as a durable epoxy resin.

Related patents include Webster
U.S. Patent No. 4.41 Otsu No. 034 (November 2, 1983)
No. 4.50a880 (April 2, 1985) and U.S. Pat. No. 4,414,372 to Fa, et al.
4.524, 196 (June 18, 1985). Also, U.S. Patent No. 4.58a7
No. 95 (May 13, 1986) discloses the use of certain oxyanion catalysts in group transfer polymerizations.

In the method of the present invention, in the polymerization, the "living" in the growing or grown polymer.
The polymer produced is characterized by the presence of a moiety containing the metal at the end, and the presence of an activated substituent or diradical or a tautomeric B-mer thereof at the "non-living" end. 1 living room.

Here used in group transfer polymerization! The monomer containing L has the formula C)(2=C(Y)X, where X' is CN, -CH=CH(JO)X"e
&2-C(0)X', and Y is -H, -CF2, -CN or 1002R, but if X is 10)I=CHC(0)X', then Y is -H or 10H3, and X' is -O8 (R')5, -R, -0R or -N
R'R' and each R1 is independently H or a hydrocarbon aliphatic, cycloaliphatic, aromatic or mixed aliphatic-aromatic group containing up to 20 carbon atoms; a group, with the proviso that R1
at least one of the radicals shall not be H; an aliphatic, cycloaliphatic, aromatic or mixed aliphatic-aromatic radical containing R&120 carbon atoms or at least two
Hydrocarbon radicals which are polymeric radicals containing all 0 carbon atoms, in which all of these groups contain one or more ether oxygen atoms in their optional aliphatic segments. °C and optionally one or more functionalities that do not react under the polymerization conditions 1;! / may contain substituents and may also optionally have the formula -Z
'(0)C-C(Y')=CH2 (in the formula, Y1 is H''!
or OR3 and Z' is 0 or (]R')'f.

and R' and R' are each independently selected from 01-4 alkyl.

The initiator used in the polymerization of the present invention is described in US Pat.
, 414,372, 4,524,196, 4.41s 031, Oyo and 4,508,880, and pending USSN 660,588,
66 (No. 1,589, No. 673,926 and No. 6)
76.099. Preferred initiators for use in the present invention are (R1)! MZ
, (R1)2M(Zl)2 and 0(M(R1)2
X') has a formula selected from 2. Here, in the formula, R1 is as defined above, and Z is the following group 8R, -〇P(NF, 'R'')2, -0P(OR1)
2, -0PCO8i(R1)3)2 and mixtures thereof, R, R1, R', B'', X' and Z' are as defined above; Z'&t-i'''-(1st!l!!-oc''''H-chv・m is 2.3 or 4, n is 3.4 or 5, M is Sl, Sn or Ga, provided that if 2 is 'kA is Sn or Ge, and R2 and R3 are each independently selected from the hydrocarbon groups defined above for H and R, and (aJ When at least one of R, R2 and R3 in the initiator is: -Z2-M(R'')3 Nikode this formula, M and B
1 is 9 as defined above, and is an activated noradical selected from mixtures thereof, R2, R3,
X', Z', m and n are as defined above and M is Sn or Ge] and/or Z2 is -Z' -C-C(P,2)(35)-, then R3 and/or G
It concerns ABA triblock polymers with standard (meth)acrylate monomers as MA) and B segments.

These methacrylate triblock polymers have now been synthesized such that the evixi groups are placed only at the ends of the polymer chains. Their backbone is (meth)acrylate (meaning acrylate and/or methacrylate)
Because of their structure, these epoxy resins are believed to exhibit significantly higher durability than conventional bisphenol A-based epoxides. These new polymers are believed to have better final properties than cyclic epoxides because the backbone is polymeric in nature. These, like bisphenol A epoxides, are believed to be superior to conventional GMA i-coalescing, which have a random arrangement of epoxy groups, since all the epoxy groups are now located at the end of the chain.

The present invention is an AEA block polymer having one central segment' sandwiched by two terminal segments, comprising:
Each terminal segment is an oxirane-containing acrylic or methacrylic moiety, providing a polymer in which the central segment is an acrylic or methacrylic moiety containing no oxirane groups.

The present invention also provides an ABA block copolymer having one central segment 4 sandwiched between two terminal segments, each terminal segment being an oxirane-containing acrylic or methacrylic moiety, and the central segment containing an oxirane group. In order to coat a copolymer with an acrylic or methacrylic moiety, the present invention provides a method in which all components are reacted using group transfer polymerization technology.

The invention relates to glycidyl (meth)acrylate (GMA or OA, ) as the A segment and standard (meth)acrylate monomers as the B segment, AEA ) rib block polymers. (
The term meth)acrylate refers to acrylate and/or
Or it includes all methacrylates. Nowadays, methacrylate triblock polymers are synthesized such that epoxy groups are present only at the terminal ends of the polymer tin. Due to the (meth)acrylate structure of their backbone, these epoxy resins are assumed to exhibit significantly higher durability than conventional bisphenol-based epoxides. These new polymers are believed to have superior final properties over cyclic epoxides because the backbone is polymeric in nature. These (well, bisphenol A
Like epoxides, all the epoxy groups are located at the end of the chain, which should provide an advantage over conventional OMA polymers in which the epoxy groups are randomly arranged.

To make an AFIA polymer according to the present invention, at least 4
There are main methods of seeds. Namely, they are: (1) Starting with a monofunctional initiator, GMA is first polymerized to create the first A segment), and then methyl methacrylate (), (MA) is added to the A segment to form AB
7] Polymerization is carried out in three steps, i.
A f polymerization completes the central B segment, and then, since it is a difunctional initiator, GMA? Monomer polymerization is carried out in two steps by simultaneously adding to both ends to form an ABAB combination = (3) Starting with a monofunctional initiator and two steps (initially () to make all the A segments) MA″f:, then make AE 7 union (MM
(4) an epoxy-containing initiator; and (4) an epoxy-containing initiator. A segment)? Starting with Il-, polymerizing MMA to form an ABB polymer, and Kurago pairing the polymers together - i.e., linking the two ABi polymers at their tB ends to form an A3A polymer;
It is.

Alkyl methacrylates and acrylates which can be used for the preparation of acrylic polymers, such as methyl methacrylate, ethyl methacrylate-1, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, include all the monomers that can be used for the preparation of the central part. Nonyl methacrylate, lauryl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, isodecyl methacrylate, propyl methacrylate, phenyl methacrylate, isobutyl methacrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isobutyl acrylate, hexyl acrylate, 2-ethyl xyl acrylate, nonyl acrylate, lauryl acrylate, stearyl acrylate, cyclohexyl acrylate, indecyl acrylate, phenyl acrylate and isobornyl acrylate, and (meth)acrylic acid monomers containing protecting groups that can be deprotected after polymerization, such as trimethylsilyl methacrylate and 1-butoxyethyl methacrylate. Both the terminal and central portions can be blinded to other functional groups, such as crosslinking functional groups, so long as this does not interfere with polymerization.

Examples 1 to 4 are (1) GMA/MIMA/GM employing a monofunctional initiator and three monomer feeding steps.
This shows how to make A epoxy resin.

Examples 5 to 11 are G! AA no EM/G
This shows how to make MA resin. Example 12 is (
31 shows how to make GMA/BMA/GMA employing a monofunctional initiator, two monomer feeds, and a coupling agent. Example 13 demonstrates how to make GMA/BMA/GMA employing (4) an epoxy initiator, -7-times 7-mer feed, and a coupling agent.

Example 1 (GMA/'MMA/C) MA 3/1
0/3) (7-no-button starter, 6-feed) 25 with mechanical stirrer, thermometer, and nitrogen inlet
Tetrahydrofuran (TH
F) (75,0gm), 1-trimethylsiloxy-
1-Methoxy-2-methylpropene (7,0 gm, 0
．． 0402M), xylene (1,0 gm), and natraphthylammonium m-chlorobenzoate (40ON of a 1.0 M solution in acetonitrile). Flask' (z cooled to 10°C. Feed I was composed of tetrahydrofuran (4,0gm) and tetraphthylammonium m-chloropenzoate (4001 Lt of 1,0M solution).
Consisting of This is added over a period of 50 minutes. Feed ■ is glycizol methacrylate (17.3 gm%G,
122 M). This starts to be supplied at the same time as supply ■. Feed ■ is added over a period of 1 minute.

Feed ■ is methyl methacrylate (4 cL 9 gm.

Feed III, which is 0.409 M), is started 6 minutes after feed I starts. Feed ■ is added over a period of 30 minutes. The temperature of the flask rises to approximately 5&0°C. After the completion of feeding Feed I, the flask is cooled to 10°C. Supply ■ is glycitul methacrylate (17.0g
m, (1120M), which is the completion of feed 1 7
The supply will start in minutes. Feed ■ is added over a period of 1 minute. When the total reaction time is 80 minutes (feed ■
22 minutes after completion of supply of methanol (1 [1,0 gm
) is added to the flask.

The molecular weight of the final polymer is number average molecular iM = 2100, weight average molecular weight ~ = 3900, polydispersity (D = -) = 1
．． 86 (theoretical MD=187[]), the conversion rate of all monomers is 99.901 or more. This resin is considered an ABA block polymer (GMA/MMA/GMA3/10/3) with three epoxy groups at each end of the resin.

Example 2 (GMpJwHyA/ayA315/3
) (7-no initiator, 6-feed) 25 with mechanical stirrer, thermometer, and nitrogen inlet
Tetrahydrofuran (THF) in a round bottom flask.
(75,6gm), 1-trimethylsiloquine-1-methoxy-2-methylzolopene (7,0gm, 0.04
02 M), xylene (1,0 gm), and tetrabutylammonium m-chlorobenzoate (1.0 M solution in acetonitrile 4001). Cool the flask to 10°C.

Feed I consisted of tetrahydrofuran (4.0, gm) and tetrabutylammonium (m-chlorobenzony) (
1, OM solution 400mz). This is added over a period of 50 minutes. Feed ■ is glycidyl methacrylate (17,3 g!+1, Q, 1221,1).

This starts to be fed at the same time as co-feed I. Supply ■ is 1
Added over a period of minutes.

Feed ■ is 2-ethylhexyl methacrylate (40,
7gm, 0.206M). The supply of the feed (■) is started 9 minutes after the start of the supply of the feed (I). Supply III is 30
Added over a period of minutes. The temperature of the flask is about 41.
The temperature rises to 0°C. After completing the feeding of Feed I, the flask was
Cool to ℃. The supply ■ is glycidyl methacrylate (
17.1 gm.

0.120M). This starts 8 minutes after the feed of Feed I is completed. Feed ■ is added over a period of 1 minute. When the total reaction time is 70 minutes (11 minutes after the completion of feed 1), methanol (to, Ogm) is added to the flask.

What is the molecular weight of the final polymer?ゎ=1800, ~=3400,
D=189 (ffi theory Mn=1870). The conversion rate of all 7-mers is 99.991 or more. This resin is considered to be an ABA block polymer (GMA/EHMMOMA 315/3) with three epoxy groups at each end of the resin.

Example 3 (GMA/balls (MA/GMA 4/40/4
) (7-no initiator, 6-feed) 25 with mechanical stirrer, thermometer, and 9-element inlet
Nomethoxyethane (Gulino) in a 07nl round bottom flask
(1a6gm), 1-trimethylsiloxy-1-1-butoxy-2-methylpropene (2.1gm, 0.00
97M), and glycidyl methacrylate (5,6
gm, 0.0394M)'.

Cool the flask to 10°C. Tetrabutylammonium m-chlorobenzoate (TEACB) (200 d of a 1.0 M solution in acetonitrile) is injected into the flask. Feed I consisted of Glino (50 gm) and tetrabutylammonium m-chlorobenzoate (1,0M solution 2
0011j).

This is started 10 minutes after the first injection of TEIACB. This is added over a period of 56 minutes.

Feed ■ is methyl methacrylate (4 [13 gm.

0.403M), which is started to be fed at the same time as feed (①). Feed ■ is added in increments of 35 minutes.

The temperature of the flask rises to approximately 590°C. After the feed of feed (1) is completed, the flask is cooled to 10°C. Supplies ■
is glycidyl methacrylate (5.9 gm, CLO4
15M). Feed m is started 42 minutes after the start of feed m. Feed ■ is added within 1 minute.

At a total reaction time of 66 minutes (completion of feed ■13
After a minute), methano-7' (5,20 gm) and toluene (t325) are added to the flask.

The molecular weight of the final polymer is M, = 5300. mw=670
0, D=1.27 (theoretical Mn=5200). The total monomer conversion rate is more than 9999 yen. This resin is believed to be an A3A block polymer (G) JA7'MMA/GMA4/40/4) with four epoxy groups at each end of the resin.

Example 4 (GMA/MMA10MA 8/40/
8) (mono-initiator, 6-feed) 25 equipped with mechanical stirrer, thermometer, and nitrogen inlet
Dimethoxyethane (Gulino) (1
7,5 gm), 1-trimethylsiloxy-1-1-butoxy-2-methylpropene (2,2 gm, 10102
M ), and glycitul methacrylate (11,3 g
m, 0.0796M) k light filling. 1 flask
Cool to 0°C. Tetrabutylammonium m-chlorobenzoate (200 ml of a 1.0 M solution in acetonitrile)
A is injected into the flask. Supplies! The feed is started 10 minutes after the first injection of Gulino (50 gm) and tetrabutylammonium m-chlorobenzoate (20 C11 of a 1,0M solution) or Ranal, cholehacitrabutylammonium m-chlorobenzoate.

This is added over a period of 56 minutes. Feed ■ is methyl methacrylate (4G, 2 gm%Q, 402M). This starts to be supplied at the same time as the supply of the supply item (■). Feed ■ is added over a period of 35 minutes. The temperature of the flask rises to approximately 6Q, 7°C. After feed (1) is completed, flask ff is cooled to 110°C. Supply ■ is glycitul methacrylate (12.1 gm% 10852M)
, the supply of the feed (■) is started 42 minutes after the start of the supply of the feed (I). Added to feed ■ within 1 minute. At a total reaction time of 66 minutes (13 minutes after completion of feed ■), methanol (5.20 gm) and toluene (1
, 118) is added to the flask.

The molecule it of the final polymer is circle = 7530, ~ = 11,20
0, D=1.49 (theoretical Mn=6200). The total monomer conversion is greater than 9,999 inches. This resin is
ABA block polymer containing 8 epoxy groups at each end of the resin (GMA/MMA/GMA 8/40/
8).

Actual trip example 5 (()MA/BMA, yrio)aA1/6
/1) (G-initiator, 2-Feed) A 250 ml round bottom flask equipped with a mechanical stirrer, thermocouple and nitrogen inlet is dried with a heat gun.

Next, tetrahydrofuran (13JJ), 1,2-bis(1-trimethylsiloxy-2-methylpropenoxy)ethane (24.0grn, 57% ethyl acetate solution) and tetrabutylammonium chlorobenzoate (1,02M acetonitrile) were added to the flask. Solution 1
．． 'lytl). Place the entire flask in a water bath and cool to 6°C. Feed I consists of tetrabutylammonium chlorobenzoate (1.2 TjIl in 1,02 M acetonitrile) and THF (58 M
).

This is added over a period of 40 minutes. Feed ■ is butyl methacrylate (57, Od, 0.359-[nyl)
was started at the same time as feed (1) and added over a total of 20 minutes. The feed ■ is glycidyl methacrylate (11,3 ml, 0.1
20 mol), which is added all at once 35 minutes after the start of feed I. After addition of feed ① the temperature rises from 7°C to 21°C. The water bath is removed 50 minutes after the start of Feed I. Water (3.2 ml) is added to the flask when the total reaction time is 80 minutes.

The molecular weight of the final product is circle = 1520. ξ=2240, D
= 1.48 (theoretical M!1 = 1334), this resin is considered to be an ABA block polymer (GMA/BMA/GMA) with one epoxy group at each end of the button.

Example 6 (C) MA/EMA/GMA 2/4/
2) (-)-Initiator, 2-Feed) A 2501ne round bottom flask equipped with a mechanical stirrer, thermocouple and nitrogen inlet is dried with a heat gun. Next, add tetrahydrofuran (13FI+/
), 1,2-bis(1-trimethylsiloxy-2-methylpropenoxy)ethane (24,0 gm, 57% solution in thiethyl acetate) and tetrabutylammonium chlorobenzoate (1,02M solution in acetonitrile 1.
2 rrl) Load f. Place the flask in a water bath and cool to 6°C. Feed l is tetrabutylammonium chlorobenzoate (t C12M acetonitrile solution t 2 m) and TE(F (4,0 ml)
Consisting of

This is added over a period of 40 minutes. Feed ■ contains butyl methacrylate (3aiuS [1240 moles), is started at the same time as feed ■, and has a total of 2
Added over 0 minutes.

Feed ■ is glycitul methacrylate (32,7rnl
.

0.2aO). This is the start of supply of feed I 35
After a few minutes, it is all added. After addition of feed ① the temperature rises from 7°C to 35°C. Start of supply of supplies ■ 50
After a minute the water bath is removed. Water (3.2 ml) is added to the flask when the total reaction time is 80 minutes.

The molecular weight of the final product is 1n = 1830, Ω = 2970
, D = 1.62 (theoretical Mn = 1334). This resin is an ABA Zollock polymer (()MA, /'BMA/CM) with two epoxy groups at each end of the chain.
A).

Example 7 (GMA/EMA/GMA 3/28/
3) (No initiator, 2-Feed) A 25[]v round bottom flask equipped with a mechanical stirrer, thermocouple and nitrogen inlet is dried with a heat gun.

Next, add tetrahydrofuran (135m/ml) to this flask.
), 1,2-bis(1-trimethylsiloxy-2-methylpropeneoxyphethane (6,4 gm, 57% solution in ethyl acetate) and tetrabutylammonium chlorobenzoate (1,045 M solution in acetonitrile (], 3at ) loaded The entire flask is placed in a water bath and cooled to 12° C. Feed I consists of tetrabutylammonium chlorobenzoate (to 45M in acetonitrile g 0.3 ml) and T) IF (4,771
J). This is added over a period of 40 minutes.

Feed ■ is butyl methacrylate (71 ml, 0.4
47 mol), started at the same time as Feed I and added over a total of 20 minutes. The feed ■ is glycidyl methacrylate (11 cJml, 1
1088 mol). This is the start of supply of supply ■3
After 5 minutes, all is added. After addition of feed m the temperature rises from 7°C to 13°C. Start of supply of supplies ■ 5
The water bath is removed after 0 minutes. Water (1, OM) is added to the flask when the total reaction time is 80 minutes.

The molecular weight of the final product is circle = 7950, QW = 10,9
00, D=1.37 (theoretical Mn=5026),
This resin has three epoxy groups at each end of the chain.
It is believed to be a BA bronc polymer (GMA/BMA/()MA).

Example 8 (GMA/BMA/GMA 3/2
/3) (G-Initiator, 2-Feed) A 250 ml round bottom flask equipped with a mechanical stirrer, thermocouple and nitrogen inlet is dried with a heat gun. Next, tetrahydrofuran (TH
F13511'17), 1,2-bis(1-) IJ methylsiloxy-2-methylpropenoxy)ethane (2
4,18ml 1574 ethyl acetate solution) and tetrabutylammonium chlorobenzoate (1,045ml
M acetonitrile solution (1.2 N) is charged. Place the entire flask in a water bath and cool to 6°C. supply 1
is tetrabutylammonium chlorobenzoate (1,
045M acetonitrile solution 1.2 ml) and T
HF (4,3N), which is added over a period of 40 minutes. Feed IN is butyl methacrylate (1
9.0 N% (0.120 mol), started at the same time as Feed I and added over a total of 20 minutes. Feed m is glycidyl methacrylate (4
9, OmjS α (340 mol), which is added in its entirety 35 minutes after the start of feed I. After addition of feed ① the temperature rises from 5°C to 46°C. The water bath is removed 50 minutes after the start of feed (1). Water (52M) is added to the flask when the total reaction time is 80 minutes.

The molecular weight of the final product is blind. =2010, Mw=4050
, p=2. Q2 (theoretical Mn=1334), this resin is believed to be an ABA block polymer (GMA/BMA/GMA) with three epoxy groups at each end of the chain.

Example 9 (GMA/BMA/GMA 3/8/
3) (No initiator, 2-feed) A round bottom flask equipped with a mechanical stirrer, a thermocouple and a nitrogen inlet is dried with a heat gun. Next, add tetrahydrofuran <6 to this flask.
75ml), 1,2-bis(1-trimethylsiloxy-
2-Methylprooxy)ethane (7!1.6 gm,
57% ethyl acetate solution 1. ) and tetrabutylammonium chlorobenzoate (17 ml of a 1,045 M solution in acetonitrile). Place the flask in a water bath and cool to 4°C. Feed I is tetrabutylammonium chlorobenzoate (1,045
M acetonitrile solution 3.7 ml) and THF
(6,7mA). This is added over a period of 40 minutes. Feed ■ is butyl methacrylate (232m
, 1.70 mol) and was started at the same time as feed (1) and added over a total of 20 minutes.

Supply ■ is glycitul methacrylate) (15omg, 1
．． 10 moles). This is the start of supply of supply ■35
After a few minutes, it is all added. After addition of feed ① the temperature rises from 13°C to 46°C. Start of supply of feed I 5
The water bath is removed after 0 minutes. Water (10.0M) is added to the flask when the total reaction time is 8M minutes.

The molecular weight of the final product is unknown. ==3230, MW=/12
70°D = 1.32 (theoretical), 4n = 2186 >, this resin is believed to be an AEA block polymer (GMA) with three epoxy groups at each end of the button (BMA/GMA).

Example 9A (Coating made from the product of Example 9) The following example illustrates how OMA block polymers are used in coatings. This polymer is blended with an anhydride-containing acrylic polymer, applied, and cured at room temperature. Curing occurs between the epoxy group and the anhydride.

The following compositions are prepared and then blended together to form an air-dry enamel.

Ingredients Parts by weight (produced in Example 9) Anhydride-containing polymer 154.4 solution (+JMA/NBA/ITA-AN 18155/27
) 36% solids [MMA-methyl methacrylate] (NEA = butyl acrylate) 1" ITA-AN = itaconic acid anhydride anoazabine clooctane catalyst Dabco) 1.
D dimethylethanolamine 1.0 toluene
121.6 Total 40Q, 0 Apply the above set 1i'j to steel stain 4 panel, 1
It was left at room temperature for a week to harden. This coating is transparent, hard (145 Chi grade in Ferzoci test), and good/! - has adhesive properties and has a gelation time of 3
It was 6 hours.

WORKING EXAMPLE 9B (Coating made from the product of Example 9) The following example () shows how MA block polymers are used to make coatings and how accelerated weathering tests of the coatings are performed. This shows how the system will be implemented. GMA polymers were cured using diamines.

The following compositions are prepared and blended together to form a vine enamel that is cured under air drying or at elevated temperatures.

(Prepared in Example 2 Ifli Example 9) Isophoronediamine ao a.

Pencil alcohol 359 - Monsanto 1i4
-Resiflov Total surfactant 314.5
100.0 The above composition was applied to a primed steel armpit for one week at room temperature or 60°C at 120°C.
It was left to cure under either condition for a few minutes.

All panels were clear, hard, and had good adhesion.

Baking No. 9 flannel has a Knoop hardness of 52 and an initial 6 of 7a4.
It had a 0 degree gloss. They were exposed to the QtJV accelerated sobriety tester. After 120 hours of QUV exposure, 6 of them
The 0 degree gloss was 7Q, 1.

Initial 60 degree temperature of 77.6 on room temperature cured panel? had. Their 60 degree gloss after 120 hours of QUV exposure is 74
．． It was 1. These results show that GMA coating
This shows that it is lit durable even if it is cured at room temperature or baked at high temperature.

Control Test 1 (Control Coating Made from Bisphenol A Epoxy) The following example is an example of a coating using a bisphenol A type epoxy. This was used as a control in an accelerated weathering test. Bisphenol A epoxy polymer was cured with diamine.

The following compositions are formulated and blended together to form an enamel that can be cured under air drying or at elevated temperatures.

(manufactured by Cal) Inphorondiamine 30.1 3G,
1 benzyl alcohol 142.7
- "Resoflow" surfactant 14.3 -
Total 256.2
10 (LO) The above composition was applied to a primed steel panel and left to cure either in a box at room temperature for one week or at 120° C. for 60 minutes.

All) 9-nels were clear, hard and had good adhesion.

Baking/J flannel has a Knoop hardness of 57 and an initial 6 of 7a5
It had a 0 degree gloss. They were exposed to the ftQU'v accelerated weathering tester. After 120 hours of QUV exposure, their 60 degree gloss was 2.6.

This indicates that this coating is not durable. The room temperature cured gloss panel had an initial 60 degree gloss of 72.0. 6 of them after 120 hours of QUV exposure
The 0 degree gloss was 2.0. These results indicate that coatings based on bisphenol A') are less durable than coatings based on GMA block polymers, whether cured at room temperature or baked at high temperatures.

Example 10 (GMA/BMA/GMA 1/12
/1) (G-1 Initiator, 2-Feed) Dry 8 oz. Laspin in oven and install solution cap. Inside this is a Hakia stirring rod, Thermocazol and? A cumulative inlet will be installed. Then,
In this bottle, toluene (33.7mJ), 1.2-bis(
1-trimethylsiloxy-2-methylpropenoxy)
Ethane (5, tgm, 57 thiethyl acetate solution) and tetrabutylammonium chlorobenzoate (1,045 M acetonitrile solution, 2 mA
). Place the bottle in a water bath and cool to 4°C. Feed material is 0.2 m of tetrabutylammonium chlorobenzoate (1,045M acetonate).
l? ) and toluene (4.13 m/).

This is added over a period of 1130 minutes. Co-feed I, containing all butyl methacrylate (17.5 M, 0.110 mol), was started at the same time as Feed I and added over a total of 10 minutes. Feed (1) consists of glycidyl methacrylate (2.5d, 0.018 mol), which is added all at once 25 minutes after the start of feed (1).

After addition of feed ① the temperature rises from 7°C to 10°C. 40 minutes after the start of feeding Feed I, the water bath is removed. When the total reaction time reached 50 minutes, methanol (CL5m
A) is added to the bottle.

The molecular weight of the final product is Mn=1690, %=2500,
D=1.48 (theoretical Mn=2186). This resin is believed to be an ABA block polymer (GMA/BMA/''GkAA) with one epoxy group at each end of the chain.

Example 11 (G>AA/BMA/GMA 2/1
0/2) (Gee Initiator, 2-Feed) Dry 8 oz. in a Rasphine oven and install a sour cap. A can stirring rod, a thermocouple, and a nitrogen inlet are installed inside the tank. Next, add toluene (35L7N) and 1.2-bis (1-
Trimethylsiloxy-2-methylpropenoxy)ethane (5,4 gm, 57% solution in ethyl acetate) and tetrabutylammonium chlorobenzoate (1,[
] 0.2jEj of 445M acetonitrile solution is fully loaded. Place the bottle in a water bath and cool to 4°C. Supplies ■
Tetrabutylammonium chlorobenzoate (1,
0.045 M a7tonitrile solution (0.2171 J) and toluene (4,811 Ll). This is added over a period of 30 minutes. Feed I contains butyl methacrylate (14.5%, 0.092 moles) and is started at the same time as Feed I and added over a total of 10 minutes. The feed ■ is glycidyl methacrylate (5
,0rILt.

0.037 mol). This is added all at once 25 minutes after the start of feeding Feed I. After addition of feed ① the temperature rises from 6°C to 13°C.

The water bath is removed 40 minutes after the start of feeding of feed ■. When the total reaction time is 50 minutes, methanol (cL
m/) is added to the bottle.

Molecular weight t of final product; circle 〒1900, ζ=3290,
D=1.73 (theoretical Mn=2186). This resin is believed to be an AEA block polymer (GMA/BMA/GMA) with two niboxy groups at each end of the chain.

Example 12 (GMA/Jin A/GkiAA 4/40/4
250 with mechanical stirrer, thermometer, two nitrogen inlets
Nomethoxyethane (Gulino) (1a) in a round bottom flask
6gm), 1-trimethylsiloxy-1-1-butoxy-2-methylpropene (2,1gm, cLOD 97
), 4), and glycidyl methacrylate (5,
6 gm, 0.0394 M).

Cool the flask to 10°C. Tetrabutylammonium m-chlorobenzony) TBACB (200! nl of a 1.0 M solution in acetonitrile) is injected into the flask. Feed 1 contains glino (3, Ogm) and tetrabutylammonium m-rioo benzoate (1, O
200ml of M solution). This is started 10 minutes after the first injection of TEACB. This is added over 56 minutes. Feed ■ is methyl methacrylate (2
0, Ogm, 0.20! , 4). It starts feeding at the same time as feed I starts. Feed ■ is added over 65 minutes. 20 minutes after the completion of supply of feed material (1), diphenyl terephthalate (1,54 g=n, 0.
0048M) is added and the reaction is left at room temperature overnight. This causes the living polymer strands to bond to each other. Then methanol C4, Dgrn) is added. It is an ABA block polymer (GMA/'kAMA/GMA) with four epoxy groups at each end of the polymer chain.
d/4 D/4).

Example 13 (GMg MA10MA f/40/1
) (250 m equipped with epoxy initiator, 1-feed, camping agent, mechanical stirrer, thermometer, and monoxide inlet)
Tetrahydrofuran (IA6gIn
), and 1-trimethylsiloxy-1-glycidoxy-2-methylpropene (2,16 gmlo, 010M
). Cool this 75 sco to 10°C. Tetrabutylammonium m-chlorobenzoate (100 InJ of 1.0 M in acetonitrile) is injected into the flask. Feed 1 fs tetrahydrofuran (4
,0gm) and tetrabutylammonium m-chlorobenzoate (1.0M solution in acetonitrile?'liO
0g), which is started 10 minutes after the first injection of TBACB. Feed #1 is methyl methacrylate (20,0gm, 1120M), which is started at the same time as Feed #2 and added over a 30 minute period. After 20 minutes of photons of feed (1), diphenyl terephthalate (1.08 gm.

0.005M)' is added and the reaction mixture is left at room temperature overnight. This causes the living polymer chains to bond to each other. It is an ABA block polymer (GMA/
νMA/GMA I/40/1).

Patent applicant: 2 people other than E.I. du Pont de Nemoers & Compagnie

Claims (1)

[Scope of Claims] 1) An ABA block polymer having two terminal segments and a central segment sandwiched between the terminal segments, wherein the terminal segments are such that the most terminal group at each end is The ABA block polymer is an oxirane-containing acrylic or methacrylic moiety, such as an oxirane group, and the central segment is an acrylic or methacrylic moiety free of oxirane groups. 2) A polymer according to claim 1, in which the terminal segments contain glycidyl methacrylate monomer units. 3) @M@_n of the center segment is 300 to 20,00
0, and @M@_n of each terminal segment
Polymer according to claim 1, characterized in that the molecular weight is in the range of 142 to 5,000. 4) A claim in which the central segment comprises one or more monomer units selected from methyl methacrylate, n-butyl methacrylate, ethylhydroxy methacrylate, lauryl methacrylate, trimethylsilyl methacrylate and 1-butoxyethyl methacrylate. The polymer according to item 1. 5) A method for producing an ABA block polymer according to claim 1, which comprises reacting each component by a group transfer polymerization technique at a temperature of 0° C. or higher. 6) a monofunctional initiator is used with appropriate monomers,
The polymerization is carried out in the following order: a first terminal segment is formed, then a central segment is formed to which this first terminal segment is attached, and then a second terminal segment is formed which is attached to this central segment. , the manufacturing method according to claim 5. 7) a difunctional initiator is used with appropriate monomers,
Process according to claim 5, characterized in that the polymerization is carried out in the following order: forming the central segment, then forming the terminal segments on both sides. 8) a monofunctional initiator is used with appropriate monomers,
The polymerization occurs in the following order: first the end segments are formed, then the central segment is formed, and then a coupling agent is added to react the two central segments to form said ABA block copolymer. Claim 5 consisting of
Manufacturing method described in Section. 9) forming said ABA block copolymer by reacting an oxirane-containing initiator with a suitable monomer to polymerize with the central segment and then adding a coupling agent to react the two central segments; The manufacturing method according to claim 5.