JPS63132914A - Hybrid acrylic star 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 The present invention relates to group transfer polymerization.
The present invention relates to star-shaped polymers consisting of functional acrylic arms having functional groups thereon and cross-linked cores prepared by condensation reaction, and to the production thereof.

1. Preparation of swollen hydrogen star polymers Star polymers derived from unsaturated hydrocarbon molecules such as styrene, butadiene, and imprene are produced by anionic polymerization to produce lithium-terminated "living" polymers, which are then synthesized into various polymers. They have been obtained by coupling "living" polymer chains by reacting them with a functional binder. This usually produces a hydrocarbon star polymer with relatively few (3-12) arms. A larger number of arms ( For example, 15-56)'! Hydrocarbon star polymers have been obtained. Both methods of producing hydrocarbon star polymers are Rubber Chem.

and Technol, (Rubber Revie
ws for 1978) Volume 51, No. 5, 406-4
36 pages (1978) B., T., Pawer and H. L., J.
Described by Fetzters.

U.S. Patent No. 4,504,881 by A. Aoki et al.
(1981) specifies that in Example 4, styrene/butadiene "living" polymers were prepared by anionic polymerization and then coupled by reaction with silicon tetrachloride to obtain a four-armed polymer with a silicon core. There is.

H6T, U.S. Patent No. 4,185,042 by Belcarra
(1980') discloses in Example 5 a polybutadiene "living" polymer is prepared by anionic polymerization, and then this "living" polymer is reacted with r-glycidoxyprobyltonomethoxysilane, thereby producing a silicon-containing polymer. A three-armed star was manufactured.

U.S. Patent No. 4,417,0 by Lukowicz, Ft.
No. 29 (1983) produced a hydrocarbon star polymer with 10 arms of the 28i class. 5 out of 10 arms are polystyrene (M,,=12300)
and a diblock of polyisoprene (My1ae52,450); a polymer. The other five arms are polyimprene (Mn-52,450). This hydrocarbon star polymer is secondary butyllithium, then styrene, then K]ll! was prepared by charging sec-butyllithium, then isoprene, then divinylbenzene at a molar ratio of divinylbenzene to sec-butyllithium initiator of 5.5:1.

Reaction of the "living" lithium sites in the next core with carbon dioxide or ethylene oxide produced carboxylic acid or human tetraxyl groups, respectively, in the core of Example 2.

U.S. Patent No. 4.07″189 by T.J., Chiofus N.C.
No. 3 (1978) specification describes diene monomers (for example,
A lithium-terminated "living" polymer derived from butadiene or isoprene) is reacted with divinylbenzene to form a 4- to 25-armed star polymer, which is then
It has been suggested that the star polymer (which is "living") be reacted with the same or different monomers to grow further polymer chains from the core. A star-shaped polymer with two types of arms is proposed in column 5, lines 40-58.

U.S. Patent No. 4.58S529, U.S. Patent No. 4,599,40
No. 0, No. 4,468,757, No. 4,588,1
No. 20 and No. 4.50, No. 466, a series of Daukekal patents are directed to highly branched non-acrylic star polymers such as polyamide or polyether condensation polymers having two or more ends per branch. Regarding. These are rDendritic Macromolecules
s:5 synthesis of 5 tarburst
Macr by DenarimersJTOrnalia et al.
Omolecules 19, 烹9.2466-246
8 (1986) K.

U.S. Pat. No. 5,975,359 (1976) by W. Perchard and H. A polydivinylbenzene microgel with 270 active lithium-carbon bonds was obtained in Example 1, which was then reacted with styrene to obtain a star-shaped polymer with 270 arms, each arm having a weight average of 17,500 Molecule 1
It had 1.

H, Eschwe (, M, L, Valensleben and H,
Die Makromolekul by Birchyard
areChemie, Vol. 173, pp. 235-239 (1973) describes the anionic polymerization of divinylbenzene using butyllithium to obtain soluble "living" microgels of high molecular weight.

These microgels were then subjected to polymerization of other septamers to obtain star-shaped polymers. The number of arms is determined by the number of active sites in the "living" microgel, which in turn is determined by the molar ratio of divinylbenzene to butyllithium initiator.

To avoid gelation, use low concentrations (e.g. 2 in benzene).
．． Polymer by H. E., E. and W., Bouchiard, Volume 16;
100-184 (March 1975) prepared a star polymer with 67 polystyrene arms and 67 polyisoprene arms by sequential anionic polymerization of styrene, divinylbenzene, and isoprene. Low concentrations of monomer were used to prevent gelation.

2 Production of acrylic star polymers Hydrocarbon star polymers, which have different arm sizes, different numbers of arms, and even two different types of arms connected to the same core. In contrast, acrylic star polymers were only capable of a limited number of structures.

Although not intended to produce star polymers, R. Melby, US Pat. No. 4,388,448 (June 14, 1983), produces glycidyl methacrylate polymers at low temperatures by anionic polymerization.

U.S. Pat. No. 4,351,924 (1982) to C.W. Andrews and W.H. Jarkey discloses acetal-terminated "living" poly(methyl methacrylate)
1.3.5- ) with lis(bromomethyl)benzene or 1,2,4,5-tetrabis(bromomethyl)benzene to produce acrylic star polymers with 6 or 4 hydroxy end arms. did.

0,W. U.S. Patent No. 4.4,17 by Quebster,
No. 034 (November 22, 1983) and Nos. 4 and 5
No. 08,880 (April 2, 1985) and W.B.
U.S. Patent No. 4 by Farnham and Y', Tsuger.
No. 414,572 (November 8, 1983) and No. 4,524,196 (June 18, 1985) each disclose that capping agents having more than one reactive site and Group transfer polymerization (group transfer polymerization) can be performed by coupling a living "polymer" or by initiating the polymerization with an initiator capable of initiating more than one polymer chain.
It has been shown that acrylic star polymers can be produced using acrylic star polymerization. Initiators are disclosed that make it possible to obtain acrylic star polymers with up to four arms. Example 5 of U.S. Patent No. 4,508,880
See ~7.

U.S. Patent No. 458,879 to I. B. Ditzker et al.
No. 5 (May 13, 1986) describes a preferred group transfer polymerization process using an oxyanion catalyst. Engineering. U.S. Patent No. 4.622 to B0 Ditzker et al.
No. 572 (198<5 years, 11311 days) describes an improved process that extends catalyst life. U.S. Patent Application No. 78 by C1S, Hutchens and A.C. Shore
No. 2,257 (September 30, 1985) The specification is GTP
describes acrylic pigment dispersants prepared by, for example, functionalized methyl submethacrylate-glycidyl methacrylate AB dispersants.

Patent Application No. 771.682, No. 771.685, No. 771,684, No. 771,685, No. 771,686 filed on September 3, 1985 by H.J. Subinelli Each specification may include core and (i
or) teaches the production of acrylic star polymers with functional groups in the arms and some crosslinking of the core. Preferably, a TP method is used in which the arms and the core are formed separately or the arms and the core are formed sequentially.

The Kuepster, Farnham et al., Ditzker et al., Hutchens et al., and Spinelli patents and applications cited above are incorporated herein by reference.

U.S. Pat. No. 4,116 to R., T.A., Elakart.
, 917 (1978) describes hydrocarbon star polymers and that small amounts of other monomers (e.g. methyl methacrylate) can be included (column 3, 22-28).
line), and that ethylene dimethacrylate can also be used as a coupling agent (column 5, lines 22-28)
suggested. A similar suggestion is made by T. E. Kiofsky, US Pat. No. 4.07, '893, cited above.

J, C), Giriotx, P., Lemb and Hi J,/J by Serotsud, Polymer Sci, Part 0, Pol
ymer Symposia 22, pp. 145-156 (1968) describes the preparation of star polymer mixtures having 5 to 26 polymethyl methacrylate arms linked to a core of ethylene glycol dimethacrylate by anionic polymerization. There is. This mixture also contained linear polymethyl methacrylate.

The paper states that although the length of the individual branches is constant, the number of branches per star is "considerably variable", resulting in extremely high polydispersity.

Uses of Five Star Polymers Hydrocarbon star polymers are used as additives to improve the impact strength of:

Polyphenylene ether resin - see U.S. Pat.
, 242,470 (1980); rubber-modified polystyrene - U.S. Pat. No. 84, A., Aoki et al., cited above.
, 304,881; and chlorinated polyvinyl chloride resin - U.S. Patent No. 4.181.6 by M.H. Lehr
No. 44 (1980).

Hydrocarbon star polymers have also been used in asphalt concrete to improve service life. See US Pat. No. RG 4,217,259 (1980) by R.
Polyetherester resins to obtain the overall balance of desired properties - U.S. Pat.
, 011, 286 (1977); and a lubricant that improves the viscosity coefficient and acts as a dispersant.
U.S. Patent No. 4,077.8 to T. E. Kiovsky
See No. 93 (1976) - added.

Hydrocarbon star polymers are also known as methyl methacrylate/styrene/butadiene copolymers, polyesters,
Used in rounding to produce thermoplastics with excellent clarity by blending with thermoplastics such as urethanes, epoxies, acrylics, polycarbonates, polyesters, etc. by E.L. Hillier, USA. See Patent No. 4,048,254 (1977).

SUMMARY OF THE INVENTION The present invention comprises a) a cross-linked core consisting of a condensation polymer; and b) at least five acrylic block polymer chains attached to the core, each consisting of an acrylic block polymer chain having a functional group at the end of the chain attached to the core. The present invention provides a hybrid star-shaped polymer consisting of two arms.

Polymers with a.acrylic block arms are prepared by reacting one or more heptamers having a functional group and a carbon-carbon double bond to provide a polymer chain that is blocked at one end and has a second functional group. a method comprising producing a polymer and b contacting the obtained polymer with at least one component selected from a catalyst and one or more other monomers that undergo a condensation reaction with the functional groups in the arms; or a, (1) an atomic group transfer initiator together with a 1a1 or more hepatomer having a functional group and a carbon-carbon double bond that can be polymerized by a group transfer polymerization method, (a difunctional group transfer initiator, and (3) producing a block polymer by reacting at least one set selected from functional group transfer initiators with one or more monomers of (1), and b. It is produced by a method comprising contacting it with at least one component selected from one or more other monomers that undergo a condensation reaction with the functional groups therein.

Preferably, the present invention provides a hybrid star polymer in which the functional group in the arm is an epoxy derived from glycidyl methacrylate.

Preferably, in the arms of the star polymers of the present invention, one carbon-carbon 2 polymerizable by group transfer polymerization
Monomers having heavy bonds and mixtures thereof (where; X is -C'N, -CH=CHC(0)X' or -c(
o) x'; Y is -H, -CH3, -CN or -C
O2R, but when X is -CH=CHC(0)X', Y can be -H or -CH39; X' is -R1, -R, -OR or -NR '
each R1 is independently 01-10 alkyl and C6-107 lyl or alkaryl; R is 01-20 alkyl, alkenyl, or alkaryl; C6-2o cycloalkyl, aryl, or alkaryl; any of the groups contains one or more ether oxygen atoms within its aliphatic portion;
and each of the foregoing groups contains one or more functional groups that are unreactive under the polymerization conditions; and each of R' and R// is independently 01-4 alkyl selected from).

More preferably, the hybrid star polymer of the present invention in the process of manufacture comprises a, with or without other monomers,
a core consisting of a polymer derived from condensation polymerization of functional groups on the arms, b, an initiator, q-2 attached to said core consisting of polymer chains derived from one or more monomers polymerizable by consisting of at least five arms and a group Q-2II- attached to C1 and/or to at least some of said arms, the group Q- being in a "living" group transfer polymerization initiator. ant at the initiation part, the group z''- is a group transfer polymerization initiator, Q-Z
Derived from the activated substituent, 2, the initiator, Q-Z, is attached to one end of the "living" polymer chain by reacting with a 7-mer with a carbon-carbon double bond, 9-group, Z" - and a group attached to the other end of the "living" polymer chain, Q-
A “living” polymer chain can be formed with The monomers may be the same or different and have a group attached to one end of the living l polymer chain, z II- and a group attached to the other end of the "living" polymer chain, Q. One large "living" polymer chain is obtained, the group Zll- is a group, 2
is the same as or an isomer thereof. As is known in group transfer polymerization, the Q-initiator is removed by quenching, for example with water or alcohol, and the polymer is no longer "living".

Also, in the production of the star polymers of the present invention, the "living" group transfer polymerization site is (R') sM- (where R1 is selected from C1-1o alkyl and C6-1o aryl or alkaryl). and M is Sl, Sn or Ge).

More preferably, in the polymers of the invention the group Q is as defined above.

In the above polymers, the groups 2 and mixtures thereof (remember; X' is 08i(R1)3
, -R, -OR or -NR/R//; each R1 is independently C? -10 alkyl and Cd-107 lyl or alkaryl; R is Cl-20 alkyl, alkenyl or alcalgenyl; C6,,2o cycloalkyl, aryl, alkaryl or aralkyl; contains one or more ether enzyme atoms within the group moiety; and any of the foregoing groups contain one or more functional substituents that are unreactive under the polymerization conditions; and Each of R' and R'' is independently selected from 01-4 alkyl, and each of R2 and RA is independently selected from H; auto-1o alkyl and alkenyl; C6-1o aryl, alkaryl, and aralkyl. ; any of said groups except H contain one or more ether oxygen atoms in its aliphatic portion; any of all the groups mentioned above except H are unreactive under the polymerization conditions 1 and 2' is O or NR' and 6; m is 2.3 or 4; n is 3.4 or 5).

To produce a hybrid star polymer, first C)
The acrylic arms are prepared by using a sub-functional block copolymer made by TP (e.g. an epoxy block: 2 polymer and a wide variety of other functional blocks that can be derived therefrom) and then adding functional segments of the starting GTP block copolymer. The cross-linked non-acrylic core is produced by using certain types of condensation cross-linking reactions, including: The self-stabilizing particles produced in this way have acrylic arms and a condensed core as opposed to stabilized particles having acrylic arms and an acrylic core (hence the term "hybrid").

The differences between all acrylic star polymers and these hybrid star polymers refer primarily to differences related to the condensed core. The condensed core obtained by the hybrid method generally has more multipolarity than the core obtained by the all-acrylic method. Therefore, core swelling, ie, core susceptibility to changes in solvent composition, may exhibit properties similar to solvent-sensitive dispersants.

This depends on the particle size during synthesis and perhaps the refractive index or cross-bond density of the core after the particles are made, and their solubility in order to control properties such as hardness and softness of the core. can be important when using differences in Core hardness/softness can have a significant impact on impact resistance and toughness, especially when these hybrid star polymers are used in various types of acrylic and non-acrylic resins.

The size, polarity, and hardness of the condensed core can be finely tuned by adjusting the size of the starting functional segment, along with the amount, type, and functionality of the crosslinking agent used.

The ability to use pre-isolated and characterized functional block copolymers as starting materials for hybrid star polymers means that the final stabilized particles can be modified using "living" non-isolated intermediates (e.g. attached It is advantageous in that it does not depend on the presence of arms (arms and unbound arms). Although the sequential nature of the process - first producing the functional block copolymer and then producing the stabilized particles - is important, it is necessary to isolate the starting functional block copolymer to produce the hybrid star polymer. Probably not. However, isolation can sometimes be beneficial.

The nature and composition of the hybrid arms can be controlled using the same methods used to prepare the non-functional segments of functional block copolymers or the arms of all-acrylic star polymers.

Particle size, polarity and energy absorption (hardness/
The property of being able to vary the softness (softness) would allow hydrocarbon star polymers to be used in hybrid star polymers along with all-acrylic star polymers.

During the production of the hybrid star polymer arms, group transfer polymerization is used. "Group transfer" polymerization refers to the polymerization of monomers having carbon-carbon double bonds with the formula Q-Z, where Z is an activated substituent that becomes attached to one end of the growing polymer molecule, Q refers to a polymerization process initiated by a type of initiator (a group that continuously moves to the other end of the growing polymer molecule as more monomers are added to the growing polymer molecule). Therefore, the monomer group, Q, initiated by the group transfer initiator, Q-Z, can therefore initiate more monomer to further polymerize. A polymer molecule having a group, Q, is referred to as a "living" polymer, and the group, Q, is referred to as a "living" group transfer polymerization site.

The term "living" is referred to herein with a Coach-John mark to indicate its specific meaning and to distinguish it from matter that is alive in the biological sense.

In particular, in the production of star-shaped polymers, U.S. Pat.
No. 4,417,034 to MfcO, J. Kuebster, and U.S. Pat. No. 4.50
No. 8,880 (patented April 2, 1985), and partially described in No. 4,524,196 (patented June 18, 1985), legal terms have been used and all such disclosures are incorporated herein by reference.

Group transfer polymerization produces "living polymers" when an initiator of formula (R1) 3MZ is used to initiate the polymerization of monomers having carbon-carbon double bonds.

In this initiator, (R1) 5MZ, two groups are activated substituents that become attached to one end of the "living" polymer molecule. The (R1) gM group becomes attached to the other ("living") end of the "living" polymer molecule. The resulting "living" polymer molecules then themselves act as initiators for the polymerization of the same or different monomers, with a Z-activated substituent at one end and (R1) 5M at the other ("living") end. generate a new "living" homeer molecule with the group. This "living" polymer may then be inactivated, if desired, by contacting it with a source of active protons, such as an alcohol. In this regard, a specific example - group transfer of a specific monomer (in this case, methyl methacrylate) using a specific group transfer initiator (in this case, 1-trimethylsiloxy-1-isobutoxy-2-methylpropane). This will be useful when considering polymerization. The reaction of 1 mole of initiator with n moles of 7-mer produces a "living" polymer as follows: The right side of the “living” polymer molecule (“
-5i(CH2)5 group on (R1)
It is a 5M group. This 1-living" polymer molecule acts as an initiator to initiate the polymerization of the same or a different heptad. Therefore, we can define the above “living” polymer as m
When contacted with moles of butyl methacrylate in the presence of an active catalyst, the following ``living'' polymer is obtained: If the resulting ``living'' polymer is then contacted with methanol, the following inactivation is obtained: The obtained polymer is preferably F! The group transfer polymerization method used by AK uses a catalyst, an initiator, and optionally a polymerization life extender. This preferred polymerization method comprises, under polymerization conditions, at least one polar supramer with (1) attached at least one active substituent or active diradical and optionally an inert polymer under polymerization conditions. Sl, Ge, having more than one type of substituent,
The pKa (DM80) of the polymerization initiating compound consisting of a four-coordinated metal selected from Sn and (II) its conjugate acid is about 5.
~24 oxyanions and suitable cations and (IiD polymerization) by delaying the effectiveness of the polymerization core catalyst and increasing the ratio of initiated to terminated polymerization. Optionally, the catalyst is a source of fluoride, difluoride, cyanide, or azide ions, or a suitable Lewis acid. good.

In a preferred method of the present invention, a monomer having a functional group and a carbon-carbon double bond is used as a group transfer initiator (R1) 3
A “living” polymer (
arm). The resulting "living" polymer is then quenched with water or an active hydrogen-containing compound and then combined with or without other monomers.
The functional groups in the arms are reacted by a condensation reaction to produce a cross-linked core.

Conceptually, the synthesis of hybrid star polymers is based on presynthesizing a functional block copolymer and then cross-linking the functional segments with a suitable cross-linking agent. Some examples of functional segments and useful cross-linking agents are shown below.

Phthalic anhydride maleic diamine, e.g. 1,6-hexamethylene diamine inphorone diamine diphenol, e.g. bisphenol A Trifluoroacetic acid Lewis acid boron trifluoride etherate (DABCO) Rate Cross linkage for virtually any epoxide It is effective as long as the agent is applied. In the case of proton- and Lewis acid-promoted cross-linking, non-polar solvents free of protonating or complexing impurities such as glyme, such as toluene, may be required.

Amine butanediol diacrylate 1,6-hexamethylene diinocyanate, 9ζ diic acid/anhydride dialdehyde/diketone methacrylate containing alcohol terminated acrylic di/marunisocyanate Examples and others used in practicing the invention The components and method are shown below.

■ Starting material A, initiator isobutyl initiator 1-trimethylsiloxy-1-imbutoxy-2-methylpropene Molecular weight: 21tL39 1-(2-)9methylsiloxyethoxy)-1-trimethylsiloxy-2-methylpropene Molecular weight: 276.52 B, Catalyst ASHF2 Tris (dimethyl ai)) sulfonium tris(dimethyl ai) bidide T EA) I P 2 Tetrabutylammonium bitide (c4H9) 4^(F2O 'rBACF' Tetrabutylammonium chlorobenzoate C, R solvent glyme 1.2 -dimethoxyethane CH30CH2ch20ch5 Other acetonitrill = CH3CN D, monomer metacrylate CH5 -O -C -C = CA2 CH5 Punishment -10α12 EHMA Metacrylate 2 -Ethyl Hexil ○ OH5OH5 OH3 1VLW = 198.29 10 reaction A. Polymerization initiator for mackerel (using “isobutyl initiator”)
Initiator fragment (nmol) Fragment cooled polymer B. Polymerization of MMA using "OH-blocked initiators" Arms prepared in Examples 1 to 4 and other similar arms'i used as GTP functional arms Examples 5 to 4
It can be used in reaction 7.

Parts, proportions, and ratios used in the examples and elsewhere are by weight unless otherwise specified.

Example 1 Preparation of a 1-high IMA//G kite (D, -40)h-4) The 100% IMA kite and solvent were dried by passing over 4A molecular sheep. 250-4 round bottom lower,
Equipped with a cooler, a temperature probe, an N2 inlet, and a mechanical stirrer, the 9 Scotch was equipped with a 1.6 B
? and 66 μj of a 1M solution of tetrabutylammonium m-chlorobenzoate in acetonitrile.

A feed containing 63 μlk of a 1M solution of tetrabutylammonium m-chlorobenzoate in acetonitrile diluted in 0.2 μl of glyme was added over 90 minutes. At the same time, MMA (15,2t/ ) and BMA (18
,8? ) was added over 30 minutes. The temperature rose to 54.4°C. 60 of the above feed
After the addition of GMA (3,7
4f) was added over 2 minutes. The reaction mixture was kept at <10° C. until the addition of Feed 1 was complete. xylene (0,1?) and methanol (t1?) 1 to 15
Added over a period of minutes. Mn=6630, d=1.1
5. Theoretical amount Mn = 5400° solid content; 458 t, epoxy titration e = 0.32 meq/f solution.

Example 2 Preparation of MMA//GMA 87//15 Block Copolymer A 250rnt, 4-neck round bottom flask was equipped with a septum temperature probe and a glass paddle stirrer. The flask was then evacuated and dried with a heat gun. After filling the flask with nitrogen, glyme (95,5r) and dimethylketene isobutyltrimethylsilyl acetal (2,1',
11.1 mmol) was added via syringe. Catalyst solution i (0.05 cc, 1M solution of cesium difluoride in acetonitrile) was also added to this mixture via syringe. Catalyst feed (α22t; C), 1 M solution of cesium difluoride in acetonitrile, 3 cc glyme) and MMA-
T-Tsumer feed (40, (1,0,4M) t- was added simultaneously with a syringe pump. A maximum temperature of 54.2°C was observed during the MMA feed (feed started at 23.9°C).

After the end of feeding (45 min), the patch was cooled to 2.5°C in a water bath and then treated with GMA 6. Of (α042M) was added all at once via addition funnel. After the addition of GMA, the batch temperature rose to 12°C (exotherm), and after a few minutes was cooled to 6°C. Catalyst Feed - The solution was held for an additional 15 minutes (total feed time 100 minutes). The water bath was removed) and the batch was stirred for an additional 90 minutes and quenched with 5,02 methanol.

Analysis result...PLC) According to K] GPC molecular weight M, = 4770 Calculation 4180 Polydispersity (Mvr/Mn) = 1.5 Epoxy Dp (by titration) = S, OC theoretical value - 3, 8) Solid content weight %-4
Example 3 Reaction of Epoxy Block Copolymer with Isophorone Diamine A 250 m three-day round bottom flask was equipped with an addition funnel, a thermocouple, and a mechanical stirrer. Toluene (2
5,or) and isophoronediamine (t5t, 0.01
9M) was prepared. Add a solution of the epoxy block copolymer in toluene (as in Example 1 or 2) to the addition funnel.
Solid content 48.5%-polyff-24,4f, 1019M
epoxy) and additional toluene (Sat).

This epoxy resin solution was added dropwise to the diamine solution over a period of 30 minutes. Slight temperature rise (from 25℃ to about 29℃)
) was observed. After standing for about 3 hours, the initially pale yellow transparent solution turned cloudy to a bluish color and a small amount of precipitate was observed.

Example 4 Reaction of Epoxy Block Copolymer with 1,6-Hexane Diamine A 250-inch, three-hole round bottom fusco was equipped with an addition funnel, thermocouple, and mechanical stirrer. This flask: yE,) solution of epoxy block copolymer in toluene (47.4% solids solution 49.!M, polymer 255?, 0.054M epoxy) and additional toluene (25.0sd) t-charged is. 1,6-hexanediamine (43F, 0.054M) in glyme (25,Of).

2 equivalents of amine) was added dropwise from the addition funnel over a period of 50 minutes. A temperature increase of 20°C was observed during this addition period. After standing for about 2 hours, the transparent source solution turned pale yellow and a small amount of precipitate was observed.

Example 5 Reaction of Epoxy Block Copolymer with Trifluoroacetic Acid A 250rnt, 3-day round bottom flask was equipped with an addition funnel, thermocouple, and mechanical stirrer. BMA/'G in this flask
Charged with MA epoxy gastric copolymer (51,32) and additional toluene (210t).

Citrifluoroacetic acid (0.3 t) was added via syringe and the mixture was left under reflux for about 2 hours. After cooling, the mixture was yellow-orange and slightly cloudy. The viscosity was higher than at the beginning of the reaction. No gel particles were observed. GPC shows that the molecular weight (M
n) and showed a polydispersity index of only 2.2.

Toluene solution of BMAD/GMA epoxy block copolymer (axsr) and trifluoroacetic acid (0,5F)
Another experiment involving the addition of acid showed a temperature increase of 3°C;
An opalescent, bluish, cloudy solution was obtained. ycm epoxy block copolymer (solid polymer 20.(1) in toluene 60.Of
) to 1: Experiments including showed a temperature increase of 1° C. but resulted in a clear polymer solution.

Example 6 Preparation of hydroxy-containing polymer Toluene 4S, 7t, IT) IF in 250 flasks
455f, 1-) 1-methoxy-2
-Methylzolocarbon toy<α0057M) and 2-trimethylcycloxyethyl methacrylate 9.51f are charged. The catalyst m-chlorotetrabenzoic acid tetrabutylacetate wMIFIEα05- in acetonitrile is then added and an exotherm occurs. Supplies! [m in acetonitrile
-1.0M of tetrabenzoic acid tetopteranmine ecum
1lfiα05- and THF 4.4 t) is started and added over 100 minutes. Supply certificate to flask [methyl methacrylate 518? ) addition begins 40 minutes after the first catalyst addition and is added over a 40 minute period. At 160 minutes, 9 t of water S and 6.3 t of isopropanol 'I are added and then heated under reflux for 1 hour. A chain block polymer is produced. Its composition is methyl methacrylate I hydroΦ diethyl methacrylate-8
9.6/10.4. The molecular weight is M□=17,000
, Mw −2 to 800.

Example 7 Reaction of Hydroxyl Polymer and Diisocyanate A 250 ml flask was charged with 50 ml of toluene. Charge Of and polymer 58.61P of Example 6. The flask is heated to reflux to remove 56.6 ft. of solvent. 1.75 t of trimethylhexamethylene diisocyanate and 4 drops of a 1-solution of diptyltin silacrate in toluene and 6α of toluene.
of and heated to reflux for 30 minutes. A hybrid star polymer is obtained. Its molecular weight is between Mn34,4
00, Mw-64,100.

In addition to the use of the hybrid star polymers of the present invention in industrial coating applications and in various uses as solvent-responsive dispersants and tougheners for the production of plastic sheets and other applications indicated above, The polymers, as well as other products made by group transfer polymerization, have many other potential uses. These include, inter alia, fibers, films, sheets, composite materials, multilayer coatings, photopolymerizable i-materials, photoresists, soil repellents and surfactants, including bioactive surfaces, adhesives, adhesion promoters and coupling agents. Includes pour, blow, spin or spray type applications. Applications include dispersants, rheology control additives, thermal strain temperature regulators, impact modifiers, reinforcing additives, hardening modifiers, and more.

Applications that also utilize low molecular weight and low two-modality polydispersity are included. The final product that utilizes the applicable properties includes:
Clear or filled acrylic sheets and coatings, including lacquers, enamels, electrocoated finishes, high solids finishes, water- or solvent-based finishes, automotive and architectural glazing, and lighting hatches and reflectors, oils with anti-fogging agents and fuel additives, outdoor and indoor graphics, including signage and billboards and traffic control equipment, reprographic products, and many others.

Claims (1)

[Scope of Claims] 1) a, a cross-linked core made of a condensation polymer; and b, at least 5 acrylic block polymer chains bonded to the core, each consisting of an acrylic block polymer chain having a functional group at the end of the chain bonded to the core. A hybrid star-shaped polymer consisting of two arms. 2) The hybrid star polymer according to claim 1, wherein the functional groups in the arms are hydroxyl groups, amines, unsaturated groups, or epoxy groups. 3) The hybrid star polymer according to claim 2, wherein the functional group is an epoxy group derived from glycidyl methacrylate. 4) Claim 1 wherein the core portion is selected from the group consisting of diacids, anhydrides, diamines, diphenols, diepoxides, polyesters, polyethers, isocyanates, dialdehydes, diketones, melamines and other cross-linking agents. Hybrid star polymers as described in Section. 5) a, 1 having a functional group and a carbon-carbon double bond
Acrylic block arm polymers are prepared by reacting one or more monomers to provide a polymer chain with a blocked functional group at one end, and b. 2. A method for producing a polymer according to claim 1, which comprises bringing the polymer into contact with at least one component selected from the group consisting of: and one or more other monomers that undergo a condensation reaction. 6) Process according to claim 5, in which the hybrid star polymer is produced by self-condensation of functional groups on the arms. 7) Claim 5 in which the hybrid star polymer is produced by condensation of functional groups on the arms with the core moiety.
Manufacturing method described in section. 8) A hybrid star-shaped polymer produced by the production method according to claim 5, wherein the functional group in the arm is a hydroxyl group, an amine, an unsaturated group, or an epoxy group. 9) The hybrid star polymer according to claim 8, wherein the functional group is an epoxy group derived from glycidyl methacrylate. 10) Claim 9 wherein the core portion is selected from the group consisting of diacids, anhydrides, diamines, diphenols, diepoxides, polyesters, polyethers, isocyanates, dialdehydes, diketones, melamines and other cross-linking agents. Hybrid star polymers as described in Section. 11) a, (1) a group transfer initiator together with one or more monomers having a functional group and a carbon-carbon double bond polymerizable by group transfer polymerization; (2) a functional group transfer initiator; and (3) producing a block polymer by reacting at least one set selected from functional group transfer initiators with one or more monomers of (1), and b. A method for producing a polymer according to claim 1, which comprises contacting the polymer with at least one component selected from a catalyst and one or more other monomers that undergo a condensation reaction with the functional groups in the arms. 12) Claim 11, wherein the functional group in the arm is a hydroxyl group, an amine, an unsaturated group, or an epoxy group
A hybrid star polymer produced by the production method described in Section 1. 13) The hybrid star polymer according to claim 12, wherein the functional group is an epoxy group derived from glycidyl methacrylate. 14) A hybrid star polymer produced by the method of claim 11 by self-condensation of functional groups on the arms. 15) A hybrid star polymer produced by the method of claim 11 by condensation of the functional groups on the arms and the core portion. 16) Claim 15 wherein the core portion is selected from the group consisting of diacids, anhydrides, diamines, diphenols, diepoxides, polyesters, polyethers, isocyanates, dialdehydes, diketones, melamines and other cross-linking agents. Hybrid star polymers as described in Section.