TW200535146A - Characteristic improvement structure and manufacturing method of acrylic product - Google Patents

Abstract

This invention provides a characteristic improvement structure and manufacturing method of acrylic product, which are an improved application and a novel manufacturing method improvement of the conventional acrylic structure. It is characterized in adding a copolymer additive with reinforcing structure capability in an ordinary manufacturing method so that reinforced acrylic material is formed by copolymerization in the acrylic polymer. Therefore, in addition to improving impact resistance, weatherability and hardness functions, a production facility with existent process can be used without the need of purchasing new equipment for reducing equipment cost. The invented acrylic material comprises a methyl methacrylate polymer and a copolymer structure derived from a general formula for copolymerizing with the methyl methacrylate polymer. The copolymer additive has a general formula as the following.

Description

200535146 V. Description of the invention (1) [Technical field to which the invention belongs] The present invention relates to a structure for improving the properties of a field acrylic product and a method for improving the same, especially a polymethyl methacrylate (methacrylate) for short. Commonly known as acrylic production technology. [Previous technology] Acrylic is a transliteration of English Acrylics, and Acrylics is a general term for acrylates and methyl methacrylates. Acrylic sheet is often referred to as polymethylpropionate (pMMA) sheet, which is polymerized from methyl methacrylate monomer (MMA). "Organic glass" comes from English 〇rganic Glass. In recent years, in some areas, all transparent plastic sheets are collectively referred to as plexiglass. In fact, this is wrong. Acrylic refers to pure polymethyl methacrylate (PMMA) material, and PMMA sheet is called Acrylic board. Acrylic has high transparency and has the reputation of "plastic crystal". And has excellent weather resistance, especially for outdoor use, ranking first among other plastics, and has a good surface, degree and gloss ′ processing plasticity is large, can be made into a variety of shapes and products required. In addition, there are many types of plates with rich colors (including translucent swatches). Another feature is that thick plates can still maintain high transparency. Polymethyl acrylate is an amorphous polymer with a thermal denaturation temperature of 74 ° C ~ 10 2. C, the advantages are 1, high optical transparency 2, good weather resistance 3, good rigidity 4, easy to dye; disadvantages are poor chemical resistance 2, long-term use temperature of 咼 93 ° C3, stress concentration, easy Shredded. Mechanical thermoforming and vacuum dichroism are common processing methods. Polymethyl methacrylate (polymethyl methacrylate) is referred to as pmma, commonly known as acrylic. Prepared by the polymerization of methyl methacrylate (MMA)

200535146 V. Description of the invention (2) Thermoplastic resins' are mostly amorphous polymers, and their molecular weight is often as high as 1 million. The main variety is a colorless solid made by bulk polymerization. It is the most excellent organic transparent material. Its light transmittance is> 92% and density is 1.19 @ / (: 1113. It can be colored. It is commonly called organic glass. It is widely used in the manufacture of optical instruments, Lighting fixtures and advertising signs. There are many kinds of PMMA σα, which is an excellent material for high-speed fighter aircraft hoods and wind-impact glass. If PMMMα made by suspension polymerization, it is mainly used for extrusion products and dentures; latex made by emulsion polymerization can be used. Manufacture of leather finishing agent (chemical πσ for leather) or treatment of fabrics (dyeing and finishing auxiliaries), can also be used as coatings; resin solutions prepared by solution polymerization are also used for coatings. PMMA produced by any method has strong Alkali resistance, aging resistance and high strength, the light transmittance is the best among various plastics. Its surface does not have the disadvantage of abrasion resistance. It can be used to add surface coating or surface crosslinking treatment. Solution. Since the 1980s, the United States and Japan are developing video discs and optical fibers that use PMMA for optical information technology. In 1984, US plexiglass sheets, molding compounds, and The market sales of extruded products reached 147kt, and the Japanese output was 135kt. In 1972, the chemists of the German company Roma-Haas Company heated and polymerized the two returning acid esters between the glass plates to form a viscous rubber-like interlayer, which Used as safety glass. When the same method is used to polymerize methyl methacrylate, a good performance plexiglass plate, namely polymethyl methacrylate, is obtained. It is the most important species in acrylic resin. In 1931, Roma-Haas started production in a factory in the United States, followed by production in the United States and the United Kingdom. In 1936, the British Bunner Chemical Industry Company developed a suspension polymerization method. Mainland China from the 1950s Production of PMMA starts in the middle.

200535146 V. Description of the invention (3) There are three main processes in the industry: casting polymerization, emulsion polymerization, suspension polymerization, etc. will be described below. '/ Yao nian ^ bulk polymerization method is widely used. The monomer and initiator are mixed and heated to pre-polymerize, and the resulting slurry is cast into an inorganic glass model of a certain thickness, and polymerized to a gelatinous state at about 40 ° C in a loop air oven with a defined wind speed. It is then polymerized at a high temperature of 9 5-110 ° C, and finally the product is obtained by demolding at room temperature. Adding additives, comonomers or cross-linking agents during compounding can improve certain properties. It is necessary to strictly control the polymerization speed when casting into a mouth shape, such as the amount of initiator, the polymerization temperature, and the wind speed, and the released polymerization heat is released in time to make the polymerization uniform. Polymerization heat, room 54kJ / mo. When the conversion rate reaches 15% ~ 20%, the thicker the organic glass appears, the greater the heat released per unit area. If it is less than the production heat and the temperature is strictly controlled, it will cause polymerization failure. The varieties of even, even warm and loose plexiglass are transparent, colored, milky, mirror, rippled, and poly. And other plates (see the following plexiglass special products), the size can reach 3 flashes-液 liquid ^ mouth monomer for emulsion polymerization in water, economical, safe, low operating viscosity, emulsion solid content of 30% ~ 50%. :, The appropriate selection of emulsifier, commonly used emulsification key is J-type persulfuric acid or persulfuric acid and so on. In this method, the monomers of the core water buoyant ts are dispersed in an aqueous medium, and the straight bead molding powder is used for two injection molding and extrusion processing. Bead diameter and: to: molding knife to the type, amount and stirring speed. Industrial products are MMA; depends on and small amounts

200535146

Styrene or methyl acrylate Its processability. In the 1960s, plexiglass sheets were extruded, and glass was developed rapidly. After its purpose is to reduce the cost and save the copolymer, the purpose is to improve the continuous plastic flat silicon (silicon) glass through the extruder. The PMMA additive can be natural rubber. (Natural rubber) 〇j rubber is enough to graft with a variety of vinyl polymers, currently studied the most acrylic methyl vinegar (MMA) and NR graft copolymerization, polymethacrylic acid A methyl ester is a good performance plastic (p MMA ), Commonly known as organic glass j · MMA grafted NR trade name MG. MG can be produced through a variety of initiation systems, such as chemical initiation, radiation, photoinitiation, etc. It can also be frozen to graft M M A and NR to produce M G without initiator. The structural change of MG is manifested in performance, large elongation, high hardness, good impact resistance, flex crack resistance and dynamic fatigue performance, as well as good adhesion = and better fillability. It is mainly used in the industry to produce hard slabs with good impact, such as the airtight inner layer in tubeless tires and the glue for tire window diffusers. And it is widely used in other fields, such as producing adhesives, used as NR reinforcing agent, used as compatibilizer of NR / PMMA blend, epoxy resin toughening agent, etc. However, natural rubber has shortcomings; because natural rubber is not resistant to water and easily oxidized, the weatherability of MMA added with natural rubber is poor. In addition, due to the addition of natural rubber, transparency will decrease, and transparent acrylic sheets cannot be produced. There are still defects in the way of making acrylic products. One of them is still to be overcome. One of them is produced by these processes. The finished product is only suitable for use

200535146 200535146 5. Description of the invention (6) In order to achieve the above-mentioned so-called objectives, the present invention provides a method for adding a copolymer of acrylic material with a specific bonding ability, which can be combined with traditional process equipment to make the original acrylic structure Improved. The structure for improving the properties of an acrylic product according to the present invention includes: a methyl methacrylate polymer; and a copolymer structure derived from the following general formula (acrylic acid ester with more than a bifunctional group, methyl acrylate), and the formazan Methyl acrylate polymer co-polymerization; C ~ C = CH2 X = H, CH3 n = 2 ~ 10 R = Aromatic, Aliphatic * Functional group: a site with a double bond that can be polymerized by free radicals, such as acrylate, methyl Acrylate. The weight percentage of the copolymer structure is 30% or less. The method for manufacturing an acrylic product with improved properties of the present invention includes the following steps: (1) drying the raw material of methyl methacrylate (PMMA) to remove water, and (2) uniformly mixing the methyl methacrylate The specific copolymer is then subjected to a molding process; wherein the specific copolymer is a copolymer structure represented by the following general formula;

Page 10 200535146 V. Description of the invention (7) 〇 R--C —C = CH5 X = H, CH3 n = 2H0 R = Aromatic, / AJiphatic The weight percentage of the copolymer structure is 30% or less. In order to allow your reviewers to further understand the features and technical contents of the present invention, 'Please refer to the following detailed description and drawings of the present invention, but the drawings are provided for reference and explanation only, and are not intended to limit the present invention. In addition, other purposes and advantages will become clear to those skilled in the art after referring to the drawings and the detailed description of the invention later. [Embodiment] In the present invention, when acrylic acid vinegar, methacrylic acid (Acrylate, Methacrylate) is subjected to a radical polymerization reaction, the following comonomers / oligomers are added, and after the reaction is completed, strong impact resistance, Polyacrylate and methacrylate with good weather resistance. The comonomer / oligomer has the following formula ... (aromatic-aromatic, aliphatic-aliphatic) 〇x = h, ch3 n = 2-10 R = Aromatic, Aliphatic The comonomer / oligomerization The principle of the addition of substances is to use the excess bonding ability of the additives to form a three-dimensional tight polymer structure in the pressing force, thereby improving

200535146 V. Description of the invention (8) Strength and chemical properties of booster acrylic products. The following examples of additives can prove and support the effect of the present invention:

TMP3E0TA

Ethoxy 1 ated Trimethylolpropane Triacrylate o

II CHrO- (CH 2CH p) jP-CH = CH 2 〇

II CH3-CH 2-C-CH P- (CH -9H -9)-^-CH = CH 2 〇

II CHr〇- [CH 2CH 2〇) τP-CHCH 2 n = 1

2. TMP9E0TA

Ethoxy 1 ated Trimethylolpropane Triacrylate 〇

II CHrO- (CH 2CH P) iP-CH = CH 2 〇

II CHrCH 2C-CH i〇 < CH -fH -§) -ς.〇Η = 〇Η 2 〇

II CHr〇 < CH 2CH 20) tP-CH = CH 2 n = 3

3. Di-TMPTA

Di-Trimethylolpropane Tetraacrylate o 〇

II II CHj = CH-C-0-CH2 CHr0-C-CH = CH2 CH ^ CH.C-0-CH2-CXH2-0-CH3-C-CH2-0-C-CH = CH2 〇〇2Η5 〇 2Η5 ◦ 4. Tri-functional urethane aery late

Page 12 200535146 V. Description of the invention (9)

R1 —0— NH 〇 -i- R2—C—NH—0-CH Factory CH 「0—C—CH = CH_ 3 5.DPHA (DI-PENTAERYTHRITOL HEXAACRYLATE) ο CHjtChJ-O-CHj 〇

II CH2-0-CCH = CH2 CH2 = CHC-0-CH2-C-CH2-0-H2C-C-CHr0-C-CH = CH2 O CH ^ CHCOCHa 〇 i2-0- (jCH = CH2 〇

6.DM-87A (Hexafunctional Aliphatic Urethane Acrylate Oligomer) 〇〇R1-0-NH--{-R2-C-NH- C—NH—0—CH2—CH2—0—C—CH = CH: N = 6 (Or 2-10, can be in this range) 7. TMPTMA (Trimethylolpropane trimethacrylate) o ch3

II I

CH2 a 0_ C a C = CH 0 ch3

II I CH3 — CH2-C—CH plant 0 — 6 -c = CH 0 ch3

CH2-0 — (ϋ—C = CH 8. TMPTA (Trimethylolpropane triacrylate)

Page 13 200535146 V. Description of the Invention (ίο) 〇

CH2-〇-C-CH = CK 0 CH〇—CK — C—CH.-CH = CH,

〇II CH, -〇-C—CH = CH, 9. Epoxy Acrylate OH 9 R 十 0-CH ^ ihl-CH 「0-C-CH = CH2 The general molding conditions are shown below, with the special copolymerization of the present invention added This condition is used at the time of drying: Dry the PWIMA bird hydrophilic hygroscopic material "raw material" and before molding-be sure to dry, generally about 90 ° C for 2-4 hours of drying melting temperature 240-280 ° C ( 460- 536 T) Molding temperature 35-80 ° C (90- 176 T) Injection rate Moderate The article formed by the method of the present invention has the following excellent data of impact resistance test: Test method: IZOD ASTM-D256 Test material: PMMA + copolymer sheet Body (..%)

Page 14 200535146 V. Description of the invention (11) Comonomer and concentration sample added in PMMA (mm) IZOD (kg-cm / cm) to add 03 0.4 TMP3EOTA 5% 03 23 TMP9EOTA 5% 03 2B DI-TMPTA 5% 027 32 Tri-FUNCTIOWAL URETHANE ACRYLATE 5% 03 2.9 TMPTA5% 03 3.0 TMPTMA5% 03 3.1 Epoxy Acrylate 5% 03 2B TMP3E0TA 10% 028 2j6 TMP9E0TA 10% 03 25 DI-TMPTA 10% 03 25 Tri-FUNCTIONAL URETHANE ACRYLATE 10 % 03 25 DPHA 10% 032 Hexafunotional Urethane Acrylate 10% 031 23 The above data has been proven through practical experiments. The range of product property improvement effects can be extended to include comonomer addition concentrations of 1 to 30 ° / 〇. It is necessary to clarify the characteristic improvement structure of an acrylic product of the present invention, which includes: a methyl methacrylate polymer; and a copolymer derived from the following general formula (acrylic acid esters having more than difunctional groups, methyl acrylate) Physical structure, and the

Page 15 200535146 V. Description of the invention (12) Copolymerization of methyl methacrylate polymer; 0 R-- C --C = C H2 X = H, CH3 n = 2H0 R = Aromatic, Aliphatic The weight percentage is 30% or less. An acrylic product according to the present invention has a structure with improved characteristics and may further include the following detailed characteristics ... if the acrylic product may have a plate-like structure; and wherein the copolymer may be one of the following compounds: TMP 3 EOT A, TMP9E0TA, Di-TMPTA, Multi-functional urethane acrylate, DPHA, Polyester Acrylate 'TMPTMA, TMPTA, epoxy acrylate, S i 1 i con Aery 1 at e; and wherein the copolymer may include a compound of the general formula 2 5 kinds of chemical compounds A part of the method of the present invention, that is, a method for manufacturing a product with improved properties of acrylic products, includes the following steps: (1) drying raw materials of methyl methacrylate (PMMA) to remove water 'And; (2) the methyl methacrylic acid methyl vinegar is uniformly mixed with a specific copolymer and then subjected to molding processing, wherein the specific copolymer is represented by the following formula (acrylic vinegar with difunctional group or more, methyl acrylate ) The copolymer structure indicated;

Page 16 200535146 ο rll R ~ · C — C = CH, X = H, CH3 n = 2 ~ 10 R = Aromatic, ^ iphatic The weight percentage of the copolymer structure is 30% or less. The manufacturing method of the characteristic improvement structure of the acrylic product according to the present invention may further include the following detailed characteristics or features: wherein the molding process may be mechanical thermoforming or vacuum forming; and wherein the mechanical thermoforming may be formed, And the drying temperature of the raw material can be 6 〇 丨 〇〇〇c, and drying ^ 2-4 hours; for the properties of the material, the hot melt temperature of the molding process is 240/28 0 ° C and the molding temperature It is 35_8 (rc; where the molding process is washing and casting bulk polymerization, emulsion polymerization or suspension polymerization. Second, through the above detailed disclosure and verification, the advantages of the present invention are as follows; through this hi: =, can greatly increase the traditional pressure Acrylic sheet and all the mature trees, plastics such as unsaturated polyester (unsatura ° broadcast _ i »polyester), acrylic resin (Acrylate resin) impact resistance, weather resistance and hardness' without traditional natural rubber The present invention can indeed achieve the intended purpose of use and has a novel application. It meets the requirements for the application for an invention patent, and proposes a gun according to the patent law. The rights of the inventors: 1. The above description is only the preferred and feasible embodiment of the present invention, which limits the present invention. Mj ~ 'Equivalent to non-so-called detention. Application * Send me a book and graphic content'. ,,, And ° are all included in the scope of the present invention.

Page 17 200535146 V. Description of the invention (14) The rights and interests of the inventor are protected. Guoguo Page 18 200535146 Schematic description [Schematic description] (None) [Explanation of component symbols] (None) 1HB1 Page 19

Claims (1)

200535146 VI. Application for Patent Scope 1. An acrylic product with improved properties, including: methyl methacrylate polymer; and copolymers derived from acrylates and methyl acrylates with a bifunctional group or more as shown below The polymer structure is co-polymerized with the methyl methacrylate polymer; OX = H, CH3 n: 2 ~ 10 R = Aromatic, Aliphatic, wherein the weight percentage of the copolymer structure is 30% or less. 2. The improved structure of the acrylic product as described in item 1 of the scope of patent application, wherein the acrylic product has a plate-shaped structure. 3. The structure of the acrylic product with improved properties as described in item 1 of the scope of the patent application, wherein the copolymer is one of the following compounds: TMP 3 EOT A, TMP9E0TA, Di-TMPTA, Multi-functional urethane acrylate, DPHA, Polyester Acrylate9 TMPTMA, TMPTA, epoxy acrylate, Silicon Acrylate. 4. The acrylic product has the improved structure as described in item 1 of the scope of the patent application, wherein the copolymer contains 2 to 5 compounds of the general formula. 5. A manufacturing method for improving the properties of an acrylic product, including the following steps: (1) drying and removing water of methyl methacrylate (PMMA) raw material; and Page 20, 200535146 6. Scope of patent application (2) The methyl methacrylate is uniformly mixed with a specific copolymer and then subjected to molding processing; wherein the specific copolymer is a copolymer structure represented by the following general formula; 〇r4c -c = ch2 X = H, CH3 n = 2 ~ 10 R = Aromatic, Aliphatic wherein the weight percentage of the copolymer structure is 30% or less. 6. The manufacturing method of the acrylic product with improved characteristics as described in item 5 of the scope of patent application, wherein the molding process is mechanical thermoforming or vacuum forming. 7. The manufacturing method of the acrylic product with improved characteristics as described in item 6 of the patent application, wherein the mechanical thermoforming is injection molding. 8. The manufacturing method for improving the properties of the acrylic product as described in item 5 of the scope of patent application, wherein the drying temperature of the raw material is 60, and the time is 2-4 hours. And the method for making 9's gluttonous structure as described in item 5 of the scope of patent application, wherein the characteristics of the molding plus product are improved and the molding temperature is 35-8 (TC. The hot W temperature is 240-28 (TC 1 0. The method for making a compact structure as described in item 5 of the scope of the patent application, wherein the characteristics of the molded product are modified, emulsion polymerization or suspension polymerization. The formula is Gengzhu bulk polymerization 200535146 VI. Designated Representative Map (1) The representative map of this case is: (none) (II) The component representative symbols of the representative map of this case are simply explained: (none) iigmi