TW499441B - Process for initiating controlled polymerisation of vinyl-containing monomers - Google Patents

Abstract

An initiator is used for initiating controlled polymerisation reactions, the initiator comprising units of the formulae (R<SP>7</SP>3SiO), (R<SP>7</SP>2SiO3/2), and/or (SiO4/2) and has at least one group -D-CR<SP>8</SP>2X, wherein each R7 is independently an optionally substituted hydrocarbon group, D is a divalent straight chain or branched alkylene group containing an oxygen or nitrogen heteratom and/or substituted by a carbonyl group, each R8 is independently an alkyl group or a hydrogen atom and X' is a halogen atom. Preferably each R7 is a methyl group and the initiator comprises two terminal D-CR<SP>8</SP>2X groups wherein each R8 is a methyl group, X is bromine and D is a group CO-NR9R10 or a group CO-(OR10) wherein R9 is an alkyl group or a hydrogen atom and each R10 is independently a straight chain or branched alkylene group. The initiator is particularly useful for initiating controlled polymerisation of vinyl containing monomers.

Description

499441 A7 B7 five

、 Explanation of the invention Q The technical scope of printing by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs This invention is about the use of initiators in controlled polymerization of anti-hemp and canine complex initiators in the controlled polymerization of vinyl-containing monomers for manufacturing. Thing. An adduct or co-invention Background of the Invention Controlled polymerization systems are of great importance in polymer chemistry due to their need for the controlled preparation of polymers with a special morphology. Example ^ The ratio of prepared monomer to initiator concentration can control the amount of polymerization obtained, molecular weight distribution, functionality, phase, and / or size structure. Knife Free radical polymerization has been an important method used commercially for the preparation of high molecular weight polymers for many years. A wide variety of monomers can be used freely: Copolymerization is used to polymerize or copolymerize in bulk, solution, emulsion, dilute liquid or dispersion under relatively simple conditions. However, one of the disadvantages of conventional free radical polymerization is the lack of control over the morphology of the resulting polymers. Methods have been proposed for controlled group polymerization. For example, WO 96/30421, WO 97/18247 and WO 98/01480 disclose polymerization methods based on atom transfer group polymerization (ATRP) which provide styrene, (fluorenyl) acrylate, and other group polymerizable monomers. Controlled group polymerization. The disclosed method includes the use of an initiation system comprising an initiator having a transferable atom or radical on a group, for example, a halo 1-phenylethenyl, 2-halopropionic acid alkyl ester, p-halomethylbenzene Ethylene, or ", ^ xylene_xylene (11) a transition metal compound, such as Cu⑴ci, cu⑴Br, Ni (O), FeCl2 or RuC12, and (iii) a C_, N_, 〇_, Sjp ligand It can be valenced with this transition metal, such as bipyridine or (alkoxy). (Please read the precautions on the back before filling this page.) 装-线 _ 499 441 A7 B7 V. Description of the invention (2) In Chem. Commun., 1999 99-100, Haddleton et al. Revealed a solid catalyst (please read the precautions on the back before filling out this page). The copper catalyst is claimed to be easy to remove from the polymer product for reuse. For the atom transfer polymerization of methyl methacrylate, ethyl 2-bromoisobutyrate is used as an initiator. WO 98/01480 also discloses the preparation and use of a polymer initiator based on polydimethylsiloxane (PDMS), For example, PDMS with hydrogen-bonded silicon atoms and ethenyl chloride based on platinum The hydrosilylation reaction introduces hydrazone chloride terminal groups. However, this pathway produces two isomers, α and A, which have different activities. This isomer represents 65% of the product's paravinyl group. The initiation of the controlled polymerization of the monomer is completely inactive, and the use of the "isomer" caused the polymer or copolymer to contain unacceptably high amounts of unreacted siloxane, which is difficult to remove due to the slow initiation of the reaction . By means of a condensation reaction, we have prepared an alternative PDMS-based polymer initiator that can initiate the controlled polymerization of vinyl monomers and produce a well-defined polymer or copolymer, as described in the prior art The PDMS-based polymer initiator is more reactive and leaves little or no unreacted siloxane remaining in the product. Detailed Description Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, the word "comprises" is used in this specification in its broadest sense to mean and cover "including" ("丨 1 ^ 111 (1 € 3 ''), the concept of "inclusive" ("(: 011 ^^ 1 ^ 1 ^ 3") and "consists of". According to the present invention, it is provided to use an initiator in Initiate a controlled polymer reaction, the initiator has at least one group _D-CR82x 'and contains the formula (R73Si01 / 2), (R72Si02 / 2), (R7Si03 / 2), and / or (Si04 / 2) Sheet-5- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 499441 Α7

5. Description of the invention (3) 疋 'wherein D is a divalent straight or branched chain alkyl group containing an oxygen or nitrogen atom and / or substituted with a carbonyl group, each R8 is independently an alkyl group or a hydrogen atom , X, is a halogen atom, and each R7 independently has a group -D-CR ^ X1 or an optionally substituted nicotyl group. The initiator can be a linear, branched, cyclic, or resinous stone sintered. R7 can be an alkyl group (such as a methyl, ethyl, propyl or butyl'pentyl or hexyl group), a substituted alkyl group (such as a fluorenyl group), and a chain alkyl group (such as an ethyl fluorenyl group) Or hexyl), an aryl (such as a phenyl), an aralkyl (such as a fluorenyl) or an alkylaryl (such as a tolyl), and preferably an alkyl. In each group -D-CR82X ', it is desirable that at least one group R8 is an alkyl group, that is, X' is preferably a second or third halogen atom, and in each group -D-CR ^ X1, Preferably, both groups R8 are alkyl groups, that is, χι is more preferably a third halogen atom. In a particularly preferred system each R8 is a methyl group. X should be a stream atom. Preferred examples of the divalent group D include --- ^ --------- Yi ^ --- (Please read the notes on the back before filling out this page) Order: Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by Consumer Cooperatives.

OR10 R9 where R9 is an alkyl group, such as a methyl group, or a hydrogen atom, each R10 is independently a linear or branched alkylene group, and r is an integer from 1 to 4 -6 This paper size applies to China National Standard (CNS) A4 specification (21 × X 297 mm) 499441 A7 _B7___ V. Description of the invention (4) The preferred initiator used in the present invention has the formula R73Si0 (SiR720) qSiR73, where R7 is as above Defined and q is zero or a positive integer, such as from 10 to 100. Particularly preferred initiators have the general formula (VIII): R7 R7 R7

I / I, I i X'R82C—D-Si-0—j-Si—〇-J ^ Si-D—CR82X · R7 R7 R7 (VI LI) where R7, R8, D, X, and q are as As defined above. Examples of initiators of formula (VIII) are: (Please read the precautions on the back before filling this page)

ON ΒΓ

B 3 N——c H31--0H3 c——si——c

Η Ν——c

B

N—H H3? H3 -si——c H c 3 H c

NIH ΒΓ 〇t 〇 04- Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs and ΒΓ

rCHS 3 9 3 Η 1 H c——s——c. Bucket i 〇Λ c—s—— ΒΓ H32H3 c—s—c H3? H3 c——s——c 7

CH 3 i H s——c ΒΓ The paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 499441

5. Description of the invention (5) wherein S is zero or a positive integer, such as from 1 to 100, and t is a positive integer, such as from 1 to 100. The initiator used in the present invention can be produced by a method comprising performing at least one group R11 of a silicon-oxygen burner and including the formula (Rll3Si〇1 / 2), (Rn2Si02 / 2), (RiiSi. 3/2), and / or (si〇4 / 2) units in which at least one group R11 is an amine, via _ or oxygen group, or an amine-, substituted by · or alkoxy- The hydrazone group and the remaining groups are each independently a group R7 as defined above and (π) in a compound E is a group capable of interacting with the amine-, hydroxy- or alkoxy · group or an amine-, A hydroxy · or alkoxy-substituted alkyl group undergoes a condensation reaction to form a divalent straight or branched chain alkylene group containing an oxygen or nitrogen atom and / or substituted with a carbonyl group, and R8 and X 'are such as A previously defined condensation reaction. The above-specified special reactants used to make the initiator, and (ii) will of course depend on the particular initiator to be made. For example, to make an initiator in which the previously defined divalent group D contains peptide bonds, the condensation reaction can be performed between an amine alkyl-substituted siloxane and a fluorenylfluorene: (Please read the Please fill in this page for attention) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs

-2HBr

As another example, if the package contains 4-D 〇 group R11lsi— 丨 R11 base value 1 1 1 R1—si 丨 R1 〇 R11—si—R11

NIH

However, the UE-based paper size of 8 papers is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 499441 A7 ___B7____ 5. Description of the invention (6) It is based on a hydroxyalkyl substituted siloxane and a The condensation reaction is carried out between fluorenyl groups:

〇 011t

(Please read the notes on the back before filling this page) The condensation reaction can be performed at or above room temperature, for example, from 50 to 100 ° C. According to the present invention, the initiator is used to initiate a controlled polymerization reaction, especially a controlled polymerization of a vinyl-containing monomer, such as described in WO 96/30421, WO 97/18247, WO 98/01480, and Chem. Commun. , 1999 99-100 (Haddleton et al.). The initiator of the present invention is capable of initiating a controlled polymerization of a vinyl monomer to produce a well-defined polymer or copolymer. It is more reactive than the PDMS-based polymer initiators described in the prior art and leaves little or no unreacted siloxane remaining in the product. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, I have found that when the initiator and a special catalyst composition are solid at room temperature and contain a transition metal or transition metal compound with an average of more than one ligand valence to this Metal or metal compound, each ligand is supported by a carrier via a divalent group R, where R is a selectively substituted CrC2 () linear, branched or cycloalkylene, arylene, alkane The use of arylene or arylene to control the polymerization of ethyl monomer is especially -9- This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 499441 A7 B7 V. Invention Explanation (7) is valid. (Please read the notes on the back before filling out this page) The transition metal can be 'for example' selected from copper 'iron' nails 'turn, pseudo' germanium, nickel, baht, nickel, manganese, vanadium, zinc, gold and silver . Suitable transition metal compounds include those having the formula MY where M is a transition metal cation and pyrene is a counter anion. M is preferably selected from Cu (I), Fe (II), Co (II), Ru (II) and Ni (II), and most preferably Cu (I). Y can be, for example, Cl, Br, F, I, No3, PF6, BF4, S04 ·, CN, SPh, SCN, SePh or triflate (CF3S03), and most preferably C 1 or B r. The catalyst composition includes an average of more than one ligand with a valence to the transition metal or transition metal compound, and suitably at least two ligands with a valence. Suitable ligands include those containing C, N, 0, P, and S ligands that can be valenced with the transition metal or transition metal compound. Examples of suitable ligands are disclosed in WO 97/47661, WO 96/30421, WO 97/18247 and WO 98/01480. Preferred ligands are those containing an organic diimine group, especially formula (I): R2 R2 (I) 1,4-diazo-1 printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, 3-丁-一 女 'Formula (II) ··

(II) -10- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 499441 A7 B7 V. Description of the invention (8) 2,2'-bipyridine, Formula (III):

The p ratio Yodo-2-compound bisimine ’Formula (IV) ·· (Please read the precautions on the back before filling this page)

Yin Yin XI Sedanone, or formula (V "

4 carbonyl aldehydes printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, where each R1 is independently a hydrogen atom, a optionally substituted linear, branched, or cycloalkyl, aryl, alkylaryl, aromatic Alkyl or halogenogen-11-This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) 499441 5. Description of the invention (9). Conveniently, R1 is a hydrogen atom or an unsubstituted Ci_Ci2 tiger group, and each R2 is independently an R1 group, a Ci_C20 alkoxy group, No. plant, CN-, or a thio group. One or more or R1 and R2 groups, whose R2 and R2 groups, can form € 5-(: 8 ring alkoxy group 'cyclofluorenyl' polycyclic alkyl group, polycyclic alkenyl group or cycloaryl group, for example, ring Hexyl, cyclohexenyl or norbornenyl, compounds of the formula (ln) i2-pyridinecarboximide may contain fused rings at their p ratios. A more preferred formula (III) contains an organic diimine A group is one in which each R2 is a hydrogen atom. The divalent group R is preferably a CrC6 unsubstituted straight or branched alkylene group, for example, a propylene group, or an aralkylene or alkylene aryl group. For example, a perylene group or a tolyl group. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The carrier can be an inorganic or organic network or polymer. A suitable inorganic network or polymer is made of Si, Zr, A1 or Ti Oxides (including mixed oxides), such as a zeolite. A preferred inorganic support is a siloxane polymer or network of the formula (R33Si01 / 2) a (R32Si〇2 / 2) b (R5Si 〇3 / 2) c (Si〇4 / 2) A unit in which each R3 is independently an alkyl group, preferably a methyl group, a hydroxyl group or Oxygen, a, b, c, and d are each independently zero or a positive integer, and a + b + c + d is an integer of at least 10. The siloxane polymer and network can use silicon-containing monomers or oligos = For example, organic functional silanes, siloxanes, and organic cyclosiloxanes have the 2 (R42SiO) e, where R4 is an alkyl group, for example, a Crq alkyl group, most of which is a methyl group, is formed by polymerization or cross-linking. A suitable organic network or polymer carrier can include any organic material whose 12 'paper size is applicable to Chinese National Standard (CNS) A4 specifications (210 X 297 public love 499441) 5. Description of the invention (10) will make the catalyst composition in the chamber Wen is solid and does not hinder any polymerization reaction. It is the catalyst composition that is intended to be catalyzed. Examples of suitable organic networks ^ Polymers include polyolefins, polyolefin compounds, oxides and glycols, polymethylmethacrylate Acrylates, polyarylenes and polyesters. The ligand may be physically or chemically linked to the carrier via a divalent group, and the $ Hy ligand is chemically bonded via a monovalent group. It is preferable to be bound to this support. For catalysis according to the present invention Hair controlled polymerization reaction of the particularly desirable catalyst composition is (VII) and are according to formula (Vl),

γ \, / Br

Vt \ 〇 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs (VI) (VII) Where the siloxane polymer or network has (R33Si〇1 / 2) a (R32Si02 / 2) b (rfsi〇3 / 2) The unit of c (Si04 / 2) d, R3, ab, c and d are as defined above and ^ is a positive integer. Those skilled in this art can make the catalyst set by known methods. -13-The ‘paper size is applicable to China National Standard (CNS) A4 size x 297 public hair

Thing. The molar ratio of the reactants used to make the catalyst composition must be such that the transition metal or transition metal compound in the catalyst composition has an average of more than one ligand to the metal or metal compound. As an example, organic diimide and amine groups containing diazobutadiene can be prepared by reacting glyoxal with an aniline derivative:

H2N ~ X where X is a leaving group, such as a hydroxyl or alkoxy group or / halogen atom, the diazonium group can then be reacted with a suitable support material and a transition metal compound to form the catalyst composition , For example: —; --------- 装 — (Please read the notes on the back before filling this page)

X

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs -14- This paper size applies to the Chinese National Standard (CNS) A4 (210 X 297 mm) 499441 Α7 Β7 V. Description of the invention (12)

+

MY +

0H 0H

Μ I Υ

(Please read the notes on the back before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs where η is as defined above. As another example, a pyridine 2-carboxalimide containing an organic diimide group of the above formula (I) 1 can be prepared by reacting ethanolamine with pyridine_2_carboxaldehyde: -15- This paper is applicable to China Standard (CNS) A4 specification (210 X 297 mm) 499441 A7 B7 V. Description of invention (13)

H0 (Please read the notes on the back before filling this page) The pyridine_ 2 _ carbaldimine can then be reacted with a suitable support material and transition metal compound as described above to form the catalyst composition. The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs has printed the catalyst composition described in detail above, which has an advantage over the one described in the prior art controlled polymerization method in that the catalyst composition is a solid at room temperature and therefore can Recovery from the polymer product is reusable and allows a high degree of control over the polymerization reaction. Particularly advantageous catalyst compositions are those which are a solid at room temperature but which have a melting point below the temperature at which polymerization takes place. Particularly effective polymerization can be performed when the catalyst composition is a fluid at the reaction temperature in the reaction mixture or the transition metal compound can be more easily incorporated into the reaction mixture to achieve the catalytic effect of the reaction. reaction. As the temperature of the product cools below the melting point of the catalyst composition after the reaction occurs, the catalyst can solidify and can be recovered from the reaction mixture. The ethylamidine-containing monomer used for the polymerization may be a methacrylic acid ester, an acrylate, a styrene, methacrylonitrile, or a diene. Examples of vinyl-containing monomers include methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, and other alkyl methacrylates. -16- Applicable to this paper size China National Standard (CNS) A4 specification (210 X 297 mm) 499441 A7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (14) and acrylic acid vinegar, including organic functional methacrylate and Acrylic acid, including glycidyl methacrylate, trimethoxysilyl propyl methacrylate, allyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, dialkylamino methacrylate Alkyl esters, and fluoroalkyl (meth) acrylates. Other suitable ethylenic monomers include methacrylic acid, acrylic acid, trans-succinic acid and esters, decomposed aconitic acid (and esters), maleic anhydride, styrene, β-methylstyrene, _Ethylene, such as vinyl chloride and fluoroacetamidine, acrylonitrile, methylpropionitrile, vinylidene di_ With the formula CH2 = C (function) 2 where the halogen can be c 丨 or F, optionally substituted butadiene Ethylene has the formula CH2 = CR5_CR5 = CH2, where each R5 is independently fluorene, a Ci_C10 alkyl group, Cl or F, acrylamide or its derivative has the formula CH ^ CHCONR% and methacrylamide or its The derivative has the formula CH2 = C (CH3) CONR62 where R6 is η, a crC6 alkyl or C1. Mixtures of different monomers can also be used. The polymerization can be carried out in an inert atmosphere, for example under argon or nitrogen. The catalyst composition may be used in an amount of from 1 to 50% by weight, preferably from 1 to 20% by weight, and more preferably from 5 to 10% by weight. By the controlled polymerization reaction initiated according to the present invention, a variety of polymers and copolymers can be manufactured, and many types of monomers can be polymerized to obtain simple polymers, random or gradient copolymers, batch copolymers, block copolymers, and functionalization. Polymers, hyperbranched and branched polymers, grafted or comb polymers, and polyoxyalkylene-organic copolymers. Polysiloxane-organic copolymers have several potential uses; for example, polysiloxane-poly (hydroxyalkylpropionate) block and graft copolymers can be used for soft contact lenses, and polyoxymethylene-amine groups Acrylic acid copolymer-17- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) Packing.--Line-499441 Ministry of Economic Affairs Printed by A7 B7, Consumer Cooperative of Intellectual Property Bureau. 5. Description of the invention (15) Can be used as antifoam and anti-dye transfer agent, and polysiloxane · amino acrylate copolymer with short amine acrylate block is available. As a fabric treating agent, poly (oxyalkylsilyl propionate) -polysiloxane and poly (epoxy glycidyl acrylate) -polysiloxane copolymers can be used in epoxy resins and can be hardened Powder coatings and sealants as additives, methacrylic acid or long alkyl acrylate-polypropylene oxide copolymers can be used in polyalkylene hydrocarbons and polyester-polyacrylic acid ester copolymers as surface modifiers or additives, and the ΑΒΑ methacrylate or acrylate · polysiloxane block copolymer Plasma was used as an oxygen barrier can be cross-linked barrier coating, phosphorus and sulfo betaine or alkyl betaines Poly Silicon oxide ionomer biocompatible, for example, for shampoo or other hair treatments. Examples The following examples will be used to illustrate the present invention. Gold Photo Example 1 &gt; Storage of odorized thiomethylamine-terminated polydimethylsilane (PdMS) A molecular initiator is provided in a magnetic stirrer, condenser and addition funnel 25.亳 (9.0 g (62.9 mmol) of tetramethylazasilylcyclopentane in N2 in a bottle in 40 ml of toluene was added dropwise at room temperature to 1,000 g of each base sealant. The PDMS (degree of polymerization (Dp) = 45) at the end is in 40 liters of toluene. After heating at 50 C for 2 hours, the volatile materials are removed under vacuum to obtain 93.0 g of a colorless liquid. By uc, 29Si NMR ^ FTIR analysis confirmed that the liquid was an amine-terminated PDMS (Dp = 45). Then, in a 100 halo flask equipped with a magnetic stirrer, condenser, and addition funnel, it was placed under 2 30 g of this amine-terminated 1 &gt; 〇] ^ 8 In 5 () ml of diethylamine, add 4 25 g (18 5 mmol) of bromoiso-18 dropwise at room temperature-This paper is a Chinese version National Standard (CNS) A4 Specification (210 X 297 mm 7 (Please read the precautions on the back before filling this page)

499441 A7 V. Description of the invention (16): Bremyl bromide is in 20 ml of toluene. The mixture was kept under stirring at 90 ° C. for H hours, then the salts were decanted and the solvent was evaporated under vacuum. The polymer was washed with methyl acetate and water. The organic phase was washed with magnesium sulfate, and the volatiles were reduced and removed to obtain 27.8 g (yield 86%) of a pale yellow liquid. This liquid version confirms the characteristics of H, 13C and 29SiNMR to form n-isoisobutanol, N-methylamino, 2-methylpropyl-terminated PDMS (Br (CH3) 2CCON (CH3) CH2CH (CH3) CH2) -). King JL Example 2-The First Solid-Supported Copper Catalyst 1 In a 100-liter bottle equipped with a magnetic stirrer and a condenser, 20.0 g (186.7 mol) of 62 ml of tetrahydrofuran were mixed. ) Of 2-pyridinecarboxaldehyde and 10.7 g (74.6 mmol) of CuBr. Add 33.5 g of 3-aminopropyltrimethoxysilane by dissolving insoluble material. The reaction was an exothermic reaction to form a deep red solution, which was allowed to cool to room temperature and then 0 g (1.9 mol) of NHJ was added and diluted in 1.7 ml of water. The solution was then heated with stirring at 60 ° F for 24 hours. Evaporate the volatile materials and the solid obtained by milling under a vacuum, wash with ether and dry in a vacuum at 80 t to obtain 45.5 g of osmium red powder (Cu (% m / m) = 8 92%, insoluble in toluene, Xylene and acetone). Μ 1 -methyl methacrylate was added 5.39 grams (53.9 mmol) of methyl methacrylate (] ^ 1 ^ eight) in 11.5 liters of anhydrous para-xylene to a schlenk tube 0.66 g of the catalyst prepared in Reference Example 2 above. The mixture was deoxygenated by a freeze-pump-thaw cycle, and then 1.0 g of the polymer initiator prepared in Reference Example 1 was added at room temperature. Heat the solution under N 2 for 6 hours at 90 ° C and set -19- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) ----------- -M Pack—— (Please read the precautions on the back before filling this page) Order .. --line · Printed by the Consumer Consumption Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 499441 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 Description of the invention (17) A sample was taken for 4 NMR analysis. The final polymer was separated from the catalyst by filtration on paper only. The polymer was dried under vacuum to obtain 3.9 g of a light-colored solid. The degree of conversion of this monomer was 59% by 1η NMR observation. The catalyst was washed with toluene and ether and dried in the air to obtain 051 g of an active steel catalyst, which can be reused for subsequent polymerization. The results are listed in Table 1 below and show a very good correlation between theoretical and experimental molecular weights and are therefore controlled polymerizations: Table 1 Time (hours) Conversion% Mnth Mn PDMS% (g / mole) (g / mole) 0 0 3710 3710 100 2 10 5710 5480 68 3 27 9110 8590 43 4 42 12160 11470 32 5 52 14130 14090 26 6 59 15450 15200 24

Mn = number average molecular weight Mnth = theoretical number average molecular weight Example 2-Recovery catalyst used in MMA polymerization

Add 4.01 g (40.1 mmol) of MMA in 8.6 ml of anhydrous p-xylene to 0.49 g of a copper catalyst in a schlenk tube from 1 round of Example above. The mixture was deoxygenated by a freeze-pump-thaw cycle and then 0.744 g of the above reference example was added! Polymer initiator prepared in. Heat the solution at ^ 2 for 24 hours at 90 ° C and take samples for ifj NMR -20- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (please first Read the notes on the back and fill in this page) Install 499441 A7 B7 V. Description of Invention (18) Analysis. The results are listed in the following Table 2 and show a good correlation between the theoretical and experimental molecular weights and are therefore controlled polymerizations: — I: ------- I installed i (Please read the precautions on the back before filling this page) Order

Table 2 Time (hours) Conversion% Mnth Mn PDMS% (g / mole) (g / mole) 0 0 3710 3710 100 4 9 5510 5350 70 6 13 6310 5990 62 24 84 20500 18700 20 Preparation of D-terminated pDMS polymer initiator 5 1 g of PDMS has _Si (CH3) 2- (CH2) 2-〇- (CH2) 3CH2OH terminal unit and a number average molecular weight of 2084 (〇4949mol OH) and 5.43 grams (0.053 moles) of triethylamine into a bottle equipped with a magnetic stirrer, condenser and 20 ml of toluene to add a funnel. At room temperature, 12.37 grams (0.053 moles) of bromobromobutyrate was added dropwise and allowed to react overnight at room temperature, then the salts were filtered off and the solvent was evaporated. The polymer was washed with toluene and water. The organic phase was dried over osmium sulfate, filtered and the volatiles were removed under reduced pressure. lH NMR confirmed: the complete disappearance of the methanol function (δ = 3.56ρριη) and printed by the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-Si (CH3) 2- (CH2) 2-〇_ (CH2) 3cH2OCOC (CH3 ) 2Br appeared at 4.19 ppm 0! As in Example 4-Preparation of a second kind of rhenium catalyst with a solid support plate In an i-liter bottle equipped with a magnetic stirrer and condenser was mixed 10.04 g (560.0 mmol) Ear) of 3_aminopropyltrimethoxysilane and 00 grams (558 2 milli-21-this paper size applies to China National Standard (CNS) A4 specifications (210 X 297)) 499441

Five Λ invention description (19) Moore) of 2-pyridinecarboxaldehyde. After stirring for 10 minutes, 268 g (186.8 mmol) of CuBr, 170.4 g (1119.4 mmol) of tetramethoxysilane, 45.2 g (2511.1 mmol) of water and 0.6 g (16 · 2) Mol) Nh4f = in the bottle. A strong exotherm can be observed to obtain a uniform dark solution at 1 ° C. After 48 hours, the solution gelled into a soft gel. The solid was aged for one week and then evaporated under vacuum to remove volatiles. The obtained solid was triturated, washed with ether and dried under vacuum at 8 (rc for 8 hours to obtain 202.5 g of a brown-red powder. Polymerization was carried out by adding 190 g (1.9 mol) of MMA in 300 ml of anhydrous para-xylene Medium to 10 grams of the catalyst prepared in Reference Example 4 above in a 500 ml schlenk tube (extracted in a soxhlet with para-xylene for 6 hours). The remote mixture was borrowed by a roll-pump-unroll Periodic deoxygenation and then heating to 90 ° C and adding 10 g or more of the polymer prepared in Reference Example 3 initiated wj. The reaction was continued at 90 C for 30 hours. Samples were taken periodically for 1 η NMR analysis. The falling liquid became very viscous during the polymerization but remained clear and the catalyst was still visible in the polymer solution. The solid catalyst was filtered off after polymerization. The degree of conversion of the monomer was 44% by 1H NMR observation , And the Mη was measured by 1H NMR to be 20,900. The catalyst was extracted with p-xylene in a soxhlet for 6 hours, which can be used for subsequent polymerization. GPC analysis of the polymer showed a narrow molecular weight distribution (Mηα / Μη = 1 29) compared Initial polysiloxane initiator (Mnth / Mn = 1.5). Example 4-MMA Polymerization Transfer Catalyst recovered 30 g (0.3 mol) of MM A in 30 ml of anhydrous para-xylene Medium-22- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) -------------- Loading-(Please read the precautions on the back before filling in this Page): Line · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 499441 A7 ------- B7 V. Description of the invention (20) to 23 grams in a 100¾ liter schlenkh tube Example 3 catalysts (extracted with para-xylene in a soxhlet for 6 hours). The mixture was deoxygenated and heated to 90 ° T by a freeze-pump_thaw cycle, and then 3 grams of the above reference example was added. The polymer initiator prepared in 3. The reaction was continued at 90 t for 4 4 hours. Samples were taken regularly for 1H nmr analysis. The solution became very viscous during the polymerization but remained clear and still visible in the polymer solution The catalyst. The solid catalyst was filtered out after polymerization. The results are not shown in Table 3 below, and the theoretical and experimental results are shown. Excellent correlation between amounts and therefore controlled polymerization: Table 3 Time (hours) Conversion% Mnth Mn PDMS% (g / mole) (g / mole) 0 0 2400 2400 100 28 22 7800 7800 30.7 44 33.5 10400 10400 23 Reference Example 5-A third solid supported copper catalyst was added by adding 5 grams (0.01 mole_NH2) of amine amidine polystyrene and 1.2 grams (0.012 mole) of pyridine carboxylic aldehyde to a storage of 50 Ml of diethyl ether was placed in a 100 ml bottle at room temperature and allowed to react under nitrogen overnight. After the reaction, a yellow powder was collected, washed with methane and toluene and dried at 65 ° C for 2 hours. 4.5 g of this powder was mixed with 1.02 g of CuBr in 50 ml of acetone and stirred until the powder all turned black. The reaction was continued under reflux of acetone for 3 hours. After the reaction, the powder was washed with water and extracted with methanol in a soxhlet for 7 hours. Solid state nC NMR confirmed the existence of imine groups and -23- This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) ------------- packing --- ( (Please read the notes on the back before filling out this page) Order: -Line-Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 499441 A7

V. Description of the invention (21) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The amine group does not exist. Example 5-Polymerization of MMA 20 ml of anhydrous p-xylene and 10 g (19 mol) of "" one eight branch of 5.3 g of copper catalyst prepared according to the above reference example 5 " Schlenk tube. The mixture was deoxygenated by a freeze-pump-thaw cycle and then heated at 90 ° C and 1.01 g of the PDMS polymer initiator prepared in Reference Example 3 above was added. At 90. The reaction was continued for 5 hours and samples were taken at regular intervals. The solution became very viscous but remained clear during the polymerization. The catalyst particles can be seen in the polymer solution. After 5 hours of polymerization, 1HNMR analysis determined 33% monomer conversion and Mn = 7100. Example 6-Polymerization of MMA Added 47.4 g (0.47 mol) of MMA in 50 ml of anhydrous para-xylene to 19.4 g of copper prepared in a 250 liter Schlenk tube according to the above reference example 4 catalyst. The mixture was borrowed one; east-pumped-decomposed; after the east cycle was deoxidized and heated at 90 ° C, 5.0 g of the polymer initiator prepared according to the above Reference Example 3 was added. The reaction was continued at 90 ° C for 4 hours under N2. Samples were taken at regular intervals for H1 NMR analysis. The solution became very viscous during the polymerization and the catalyst was still visible in the polymer solution. The results are listed in Table 4 below and shown in the very good correlation between the theoretical and experimental molecular weights and are therefore controlled polymerization: -24- This paper size applies to the Chinese National Standard (CNS) A4 (210 X 297 mm) • ----------- IIII (Please read the note on the back? Matters before filling out this page) -i line · 499441 A7 ____B7 V. Description of the invention (22) Table 4 Time (hours) Conversion ° / 〇Mnth (g / mole) Mn (g / mole) PDMS% 0 0 960 960 100 32 0 960 960 100 60 21 2850 2960 32.3 123 65 6811 7760 12.6 182 84 8522 9360 10.3 237 95 9512 10760 8.9 ----- --------- Install --- (Please read the precautions on the back before filling this page) Reference Example 6 _ Preparation of PDMS polymer initiator with pendant bromoisobutyrate group 1 Set 80.5 Gram of dimethylethoxy-terminated dimethylmethyl (aminopropyl) siloxane has a degree of polymerization of 100 and 0.018 mole of NH2, and 100 ml of p-xylene to a dropping funnel, A 500 ml 3-necked reaction flask with a thermometer and a magnetic stirrer. After homogenization, 3.35 ml (0.024 mol) of triethylamine was added and 5.53 g (0.024 mol) of bromoisobutylamidine bromide was slowly injected at room temperature. The reaction was allowed to proceed at 50 ° C for 3 hours with stirring. After the reaction, p-xylene was evaporated and 300 ml of n-hexane was added to kill the triethylamine salt. This step is followed by filtration and evaporation to remove hexane. The product is a clear yellow, very viscous polymer. The disappearance of amine functionality was confirmed by 1H NMR spectroscopy. The gain of CH2CH ^ NH2 was shifted from 3.99 ppm to 3.30 ppm and a new signal corresponding to _NE_COC (CH3) 2Br appeared at 6.99 ppm. The bromination yield = 100% although some terminal ethoxy groups are hydrolyzed. -25- This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 male f) — • Line · Printed by the Consumer Consumption Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 499441 A7 _____B7 V. Description of Invention (23) 7-Preparation of a fourth solid supported copper catalyst (please read the precautions on the back before filling this page). Place 246 g (1.37 mol) of aminopropyltrimethoxysilane and 300 ml of -One toluene in a 2000 ml three-necked reaction flask equipped with a dropping funnel, a thermometer and refluxing in a condenser. Then, nick (4.16 moles) of water was added during 60 minutes while the methanol was distilled off. After the methanol was removed, para-xylene was removed under reduced pressure to give a white brittle solid. Then 84 g of this solid and 300 ml of para-xylene were placed in a 1000 ml reaction bottle and 70 g (1.0 mole) of 2-pyridinecarboxaldehyde was slowly added under cooling. After the 2-pyridinecarboxyaldehyde was added, 57 grams of CuBr was added under vigorous agitation to keep the temperature below 3. This agitation was maintained until the green characteristic of free Cu⑴ disappeared completely. After the reaction, the solid was separated from the solvent, washed with toluene and used for further purification. Theoretical CuBrw / w% = 29. Example 7-MMA's Consortium of Intellectual Property Bureau, Ministry of Economic Affairs, Employee Consumer Cooperative, printed 2.65 g (0.76 mol) above of the catalyst prepared in Reference Example 7 and 4.85 g (1.2 mol) above the reference example The polymer initiator prepared in 6 was placed in a 250 ml Schlenk bottle. The contents of the bottle were dried at 80 ° C to remove oxygen and then capped with nitrogen. 28 grams of MMA were then added under nitrogen. The mixture was deoxygenated by three freeze-thaw pumping cycles in liquid nitrogen. The bottle was then quickly heated in an oil bath to a reaction temperature of 90 ° T. The viscosity increases during the polymerization reaction and the solid particles of the catalyst remain as a suspension in the polymer solution. After polymerization, the polymer solution was filtered, residual monomers were evaporated and the polymer was analyzed by iH NMR and / or SEC to determine number average molecular weight and polydispersity. The theoretical degree based on 100% monomer conversion and polymer initiator complete conversion 'polymerization is 233. Calculated from iH NMR, 4 -26- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 public love) 499441 Printed by A7 ____B7___ of the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. The description of the invention (24) hours The experimental degree of polymerization was 113. 1,8-Bromoisobutyrylamidine-functional MT grease polymer triggers the problem | 100.0 g under N2 in a 5⑼ml bottle equipped with a magnetic stirrer's condenser and an addition funnel (L45 Mo Ear) of MeSi03 / 2 resin containing 3.6% by weight of a solution of 011 functionality in 200 liters of toluene, 32.2 grams (225.2 millimoles, in excess) of tetramethylazasilyl at room temperature was added dropwise dropwise. The% pentamine was in 50 liters of toluene. After heating at 60 ° C for 1 hour, the volatile materials were removed under a vacuum to obtain U4Og of a colorless liquid. The nc 29Si NMR and FTIR analysis confirmed that the liquid was an amine-functional butadiene resin with 4.75% by weight i-NMeH functionality. Then, 112.7 g of the amine-functional MT resin in a 500 ml bottle equipped with a magnetic stirrer, a condenser, and an addition funnel were added dropwise dropwise at room temperature in 200 ml of triethylamine under N2 at room temperature. G (217.5 mol, over 1) of bromoisobutylfluorenyl bromide in 150 liters of toluene. The mixture was kept under stirring at 60 ° C for 2 hours, then the salt was filtered off and the solvent was evaporated under air. The functionalized MT resin was washed with toluene and water. The organic phase was dried over magnesium sulfate, and the volatiles were filtered and removed to obtain 10.82 g of a yellow viscous liquid. The 1Η, 13C and 29Si NMR characteristics of the liquid confirmed the N-bromoisobutylfluorenyl, N-methylamino, 2-methylpropyl functional Mτ resin (Br (CH3) 2CCON (CH3) CH2CH (CH3) CH2)-) Contains 9.89 weight. Of

Br 〇Refer to Example 9-The fifth kind of copper catalyst supported by profit is made of 50 grams (279.3 millimoles) of aminopropyltrimethoxysilane and 200 liters. The paper size is applicable to Chinese national standards (CNS ) A4 size (210 X 297 public love) (Please read the precautions on the back before filling this page)

499441 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (25) Para-xylene is placed in a 500 ml three-necked reaction flask equipped with a dropping funnel, a thermometer and reflux. Join in 60 minutes! 8 grams (1.25 mol) of water were distilled off at the same time. After the methanol was removed, the para-xylene was removed under reduced pressure to give a white solid. Then 200 ml of toluene was added to the solid, and the bottle was equipped with a Dean & Stark device. Water was left from the reaction for a total of 4 hours by heating at 12 0 C for 4 hours. The toluene was removed under vacuum to produce a white brittle solid which was extracted with para-xylene in a Soxhlet extractor for 4 hours, followed by drying in a vacuum oven at 120 ° C for 4 hours. 10 grams of this white solid and 50 liters of p-xylene were placed in a 250-mL reaction flask and 8.6 grams (69.9 mmol) of 2-pyridine leptylaldehyde was slowly added and left to react overnight. A light colored solid was recovered by filtration and washed with p-xylene. Place 8.6 grams of the orange solid, 3.5 grams (: 1 ^ 1 »(24.5 mmol), and 30 ml of para-xylene in a 100 ml bottle and heat at 80 t for 4 hours. After cooling, the solvent was colorless and free of green CuBr. The reaction product was filtered to obtain a black solid which was extracted with para-xylene in a Soxhlet extractor for 4 hours and in an air oven at 5 Dry at 0 ° C for 6 hours. (Theoretical CuBr% (w / w) = 35). Example 8-Polymeric weighing of 2.7 g (1.17 millimolars) of MMA The polymer initiator prepared in Reference Example 8 and 3.55 Grams of the catalyst prepared in Reference Example 9 into a schienk container and deoxidized by exposure to air for 30 minutes. Under nitrogen, add 23.6 grams (0.236 moles) of distilled methyl propionate and three freezers. -Pumping-Solution-28- (Please read the precautions on the back before filling out this page) Packing-line · This paper size applies to China National Standard (CNS) A4 (21〇X 297 public love) 499441 A7 B7_ V. Description of the invention (26) Deoxidation during the freezing cycle. Heat the solution at 90 ° C for 195 minutes and remove the sample. During this time, the solution became highly viscous, which prevented the sample from being taken out. After 195 minutes of polymer conversion, the monomer conversion was measured by 4 NMR to be 77%. (Please read the precautions on the back before filling this page.) Intellectual Property Bureau, Ministry of Economic Affairs Employee Consumer Cooperative Printed Farm-29- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)

Claims (1)

499441 Chapter 89105484 The Lulu application, please publish the revised version (January 91) AB c D 5 February 11 9 This is a full range of repairs 1 · A kind of control used to trigger ethyl acetate-containing monomers A method for polymerization reaction, which comprises contacting a material to be polymerized with an initiator, wherein the initiator has at least one group -D_CR82Xf and contains formula (R73Si01 / 2), (R72Si02 / 2), (R7Si. 3/2) and / or (Si〇4 / 2) units, where D is a divalent linear or branched alkylene group containing an oxygen or nitrogen atom and / or substituted with a carbonyl group, each R8 is independent Is an alkyl group or a hydrogen atom 'X' is a halogen atom, and each R7 is independently a group -D-CR82X f or a selectively substituted hydrocarbon group. 2. The method according to item 1 of the scope of patent application, wherein at least one group R8 in each group CR 2X ′ is a alkynyl group. 3. The method according to item 2 of the scope of patent application, in which each of the groups -D-CR82X, R8 in both groups is a alkynyl group. 4. The method according to any one of claims 1 to 3, wherein the initiator has the formula R73Si0 (SiR720) qSiR73, where R7 is as defined above and q is zero or a positive integer. 5. The method according to item 4 of the scope of patent application, wherein the initiator has the formula (VIII): R / R7 • D—Si—〇. R7 X'Rs C-—Si—Ό—Si-D—CR82X 'U / q IR / R7 (VIII) where R7, R8, X, D and q are as previously defined. 6. The method according to item 1 of the scope of patent application, wherein each R7 is a C C6 alkyl group and D is selected from the group: This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 499441 8 8 8 8 AB c D OR10 r 0 human / R10 / N R9 where R9 is an alkyl group or a hydrogen atom, each R1G is independently a straight or branched chain alkyl group, and r is an integer from 1 to 4. 7. The method according to item 6 of the patent application, wherein the initiator is selected from This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)