WO1993003076A1 - Acryliques resistant a des temperatures elevees - Google Patents

Acryliques resistant a des temperatures elevees Download PDF

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Publication number
WO1993003076A1
WO1993003076A1 PCT/US1991/005641 US9105641W WO9303076A1 WO 1993003076 A1 WO1993003076 A1 WO 1993003076A1 US 9105641 W US9105641 W US 9105641W WO 9303076 A1 WO9303076 A1 WO 9303076A1
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WO
WIPO (PCT)
Prior art keywords
temperature
composition
monomer
maleimide
mixture
Prior art date
Application number
PCT/US1991/005641
Other languages
English (en)
Inventor
Jyi-Sheng Jason Shen
Original Assignee
Ici Acrylics, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to US07/322,615 priority Critical patent/US5073615A/en
Priority claimed from US07/322,615 external-priority patent/US5073615A/en
Application filed by Ici Acrylics, Inc. filed Critical Ici Acrylics, Inc.
Priority to JP4502799A priority patent/JPH06506962A/ja
Priority to BR919107027A priority patent/BR9107027A/pt
Priority to CA002093636A priority patent/CA2093636A1/fr
Priority to EP19920901995 priority patent/EP0557457A4/en
Priority to PCT/US1991/005641 priority patent/WO1993003076A1/fr
Priority claimed from CA002093636A external-priority patent/CA2093636A1/fr
Priority to US07/931,763 priority patent/US5319043A/en
Publication of WO1993003076A1 publication Critical patent/WO1993003076A1/fr
Priority to US08/020,294 priority patent/US5328962A/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/36—Amides or imides
    • C08F222/40—Imides, e.g. cyclic imides
    • C08F222/402—Alkyl substituted imides

Definitions

  • the present invention relates to high temperature heat resistant acrylic polymers preferably made through free radical polymerization of methyl methacrylate (MMA) and related acrylates with maleimide (MI) and related.maleimides through an extremely high conversion bulk polymerization process to produce extremely pure, improved acrylic copolymers.
  • MMA methyl methacrylate
  • MI maleimide
  • the acrylic copolymers of the present invention have approximately the same physical properties as conventional acrylic polymers except that the present invention polymers have high purity, a higher glass transition temperature, better impact resistance, higher heat distortion temperatures, and in the case of preferred polymers, excellent clarity.
  • acrylics are well known and have excellent optical properties and weatherability for numerous uses such as in lighting fixtures, automobile tail light lenses, dials, video discs, ophthalmic contact lenses and numerous other articles where durable, weatherable, clear features are desired.
  • PMMA Poly (methyl methacrylate)
  • acrylic industry at present.
  • PMMA has excellent weather resistance, durability and is pleasing in appearance when formulated into relatively thick sections. These features render PMMA and related acrylics ideal for such end uses.
  • the term transparent refers to the property of the copolymers of the present invention to be transparent to light and specifically refers to the fact that the preferred copolymers of the present invention have transparency properties about the same as the transparency properties of conventional PMMA.
  • the heat distortion temperature (HDT) of PMMA copolymers is satisfactory for most uses for relatively short times at temperatures of 90-102 * C (195-295 * F).
  • the glass transition temperature (Tg) of PMMA copolymers- is generally between 85-105 * C.
  • the glass transition temperature and heat distortion temperature of conventional copolymers are unsatisfactorily low.
  • the above-stated need for a high temperature acrylic has been satisfied by the present invention which encompasses a copolymer using methacrylate and maleimide group monomers.
  • the acrylic copolymers of the present invention are manufactured in a specially designed bulk polymerization process having extremely high conversion rates for the methacrylate and maleimide group monomers.
  • the final methacrylate- maleimide group copolymers are transparent without phase separation and have superior heat resistance properties compared to commercial PMMA, based on HDT and Tg data.
  • the MMA/MI copolymers of the present invention can be made in a wide range of molecular weights and with a wide range of acrylate group monomers and a wide range of maleimide group monomers.
  • phase separation refers to a phenomenon found, especially, in extremely high conversion copolymerization processes, that is, where the conversion rate is about 98% or above.
  • One of the unusual features of the preferred copolymers of the present invention is their ability to avoid phase separation at such extremely high conversion rates.
  • phase separation refers to the cloudy appearance of a copolymer, currently believed to be caused by light scattering due to the different refractive indices of the monomers used in the polymer mixture and the domain size phenomenon as described in J. Shen, Ph.D dissertation entitled "Microphase
  • Methacrylate group monomers such as methyl methacrylate and ethyl methacrylate
  • maleimide group monomers such as maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide and N-cyclohexylmaleimide
  • aerylate group monomers such as ethyl aerylate, butyl aerylate and propyl aer late, can be mixed as (I, II, III) or (I, II) or (II, III) mixtures, to provide copolymers with two or three or more different constituent monomers.
  • the first initiator is a low temperature initiator having a half-life of approximately 10 hours in the temperature range of 50-70 * C and the second initiator is a high temperature initiator having a half-life of approximately 10 hours at temperatures between 90-130 * C.
  • the low temperature initiators can be, for example, lauroyl peroxide, benzoyl peroxide, decanoyl peroxide, isononanoyl peroxide, and propionyl peroxide as well as others known to be equivalent to those of ordinary skill in the acrylic polymer art.
  • the second, or high temperature, initiator can be, for example, 2,5-dimethyl-2,5-di(t-butylperoxy) hexane, t-butylperoxy isopropyl carbonate, t-butyl peracetate, t-butyl perbenzoate and dicumyl peroxide, as well as others known to be equivalent by those of ordinary skill in the acrylic polymer art.
  • mercaptans are used in the present process for controlling the chain lengths, that is, the molecular weights, of the copolymer.
  • Mercaptans such as n-dodecyl mercaptan, n-butyl mercaptan, t-butyl mercaptan and others known in this art may be used in the bulk polymerization process of the present invention.
  • Additives such as internal lubricants, external lubricants, ultraviolet (UV) absorbers, processing aids, antioxidants, dyes, thermal stabilizers and other additives known to those of ordinary skill in the acrylic polymer art may be added to the process ingredient mixture depending on the need and physical properties desired with respect to the end use of the particular copolymer.
  • Preparation of the finished polymer involves thoroughly mixing the chosen monomers, initiators, mercaptans and additives desired. The mixing is conducted in a stainless steel container or tank and mixing continues to insure that all ingredients are thoroughly dissolved. The mixture is then purged with nitrogen gas for 20-30 minutes prior to filtration through a 0.2 micron nylon 66 or TeflonTM filter. A 20+ psi vacuum is then applied to the mixture for approximately 20 to 30 minutes to purge remaining gases and then the mixture is transferred to a nylon 66 or nylon 6 polymer cell for polymerization. The cell is similar in appearance to a large plastic trash bag and its dimensions are dependent upon the amount of mixture intended to be placed in the bag for polymerization.
  • the copolymer cell or bag .dimensions are chosen to insure uniform temperature distribution within the block or mix during the baking or polymerization step of the manufacturing process.
  • a typical thickness of the nylon bag film or wall is about 1-3 mils for a bag thickness of no more than 1-1/4 inches, although other dimensions may be used in specific processes.
  • the bag dimension and wall thickness of the bag are chosen to and function to provide relatively high surface area on the bag peripheries to maximize removal of the exothermic heat of reaction and thus maintain a low temperature drop between the monomer mixture-filled bag and the oven temperature during, especially, those periods when the polymerization reaction is taking place at its fastest rate.
  • the bulk polymerization process of the present invention uses a constant temperature reaction chamber, wherein at the beginning of the process heat is added to initiate the reaction, and later during the polymerization reaction heat is removed to prevent bubble formation in the reacting mixture, and later additional heat is added to force the reaction to extremely high conversion rates.
  • the temperature within the reaction chamber is controlled by supplying heat to the chamber at various times during the polymerization process, and supplying cooling to the chamber at other times during the polymerization process.
  • the time-temperature profile for a given polymerization process is controlled through a microprocessor system.
  • the final, bulk polymers produced have a very smooth appearance and no irregular, or "hot spot" surfaces. They also exhibit glass transition temperatures of approximately 105°C to 131°C with increasing fraction of MI content. These are superior glass transition temperatures compared to glass transition temperatures of approximately 85-105°C for conventional PMMA copolymers.
  • the final copolymers of the present invention generally comprise 90 percent or more of MMA fraction and up to about 10 percent MI fraction of the monomer mixture in the copolymer.
  • the low value of maleimide composition in copolymers of the present invention is based on the fact that approximately 11 percent by weight maleimide may be dissolved in methyl methacrylate at room temperature. Should mixing take place at higher temperatures, the relative proportions of methacrylate and maleimide monomers can be adjusted.
  • the value of MI composition is a function of solubility of the particular maleimide chosen in the particular methacrylate or acrylate chosen.
  • Figure 1 is a block diagram of the bulk polymerization process of the present invention.
  • the starting materials for the copolymers of the present invention include monomers, high and low temperature initiators, chain transfer agents, and optional additives such as lubricants and UV-absorbers.
  • the acrylic copolymers of the present invention include two or three monomer component acrylic polymers.
  • the first monomer typically is a metl ⁇ acrylate monomer such as methyl methacrylate or ethyl methacrylate.
  • the second monomer is a maleimide monomer such as maleimide, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide or N-cyclohexylmaleimide.
  • the third monomer is an acrylic monomer, such as ethyl aerylate, butyl acrylate or propyl acrylate.
  • the first, second and third monomers may be mixed in combinations of either first, second and third, or first and second, or second and third to form the basic monomer mixture. This mixture is used in preparing a specific acrylic polymer of the present invention.
  • the preferred methacr of the present invention is methyl methacrylate, whose structural formula is shown below:
  • PMMA poly (methyl methacrylate)
  • the first initiator is a low temperature initiator having a half-life of about 10 hours at temperatures between 50-70°C
  • the second initiator is a high temperature initiator having, a half-life of 10 hours between temperatures of 90-130°C.
  • the low temperature initiator may be, for example, lauroyl peroxide, benzoyl peroxide, decanoyl peroxide, isononanoyl peroxide, propionyl peroxide or other low temperature initiators known in the acrylic polymer arts.
  • the high temperature initiator may be, for example, 2,5-dimethyl-2,5 di(t-butylperoxy) hexane, t-butylperoxy isopropyl carbonate, t-butyl peracetate, t-butyl perbenzoate, dicumyl peroxide and other high temperature initiators known in the acrylic polymer arts.
  • chain length controlling additives In order to control the chain length or the molecular weights of the specific polymer, chain length controlling additives must be used.
  • mercaptans such as n-dodecyl mercaptan, n-butyl mercaptan, t-butyl mercaptan and others known to be equivalent to those in the acrylic polymer arts may be used.
  • the bulk polymerization system 1 has a feed funnel 2 for introduction of the raw material mixture including the monomers, initiators, chain transfer agents, and additives.
  • the mixture is fed through funnel 2 to a conventional compounding tank 3 where the ingredients are thoroughly mixed.
  • the mixed ingredients are then passed through a 0.2 micron filter 4 which is made of, preferably, nylon 66 or TeflonTM to remove essentially all undissolved impurities having a diameter greater than 0.2 micron.
  • the preferred filter is sold under the tradename ULTIPOR N ⁇ by Pall Puerto Rico, Inc., Fajardo, Puerto Rico, USA 00648.
  • the filtered raw material mixture is then fed to a vacuum tank 5.
  • Vacuum pump 6 draws a vacuum on the tank 5 for approximately 20-30 minutes to establish and maintain a vacuum of 20+ psi to draw off oxygen, air and other gaseous impurities that may be found in the mixture.
  • the mixture is then placed in a plurality of bags 7, also known as cells 7.
  • the cells or bags 7 are preferably made of nylon 66 film and are selected in size of the cell and thickness of the cell wall or film so as to provide relatively high surface area for the mixture contained within the bag, and to provide a clean container in which the polymerization reaction takes place.
  • the thickness of the filled bag should be less than 1-1/4 inches after a particular bag has been filled with mixture from the tank 5.
  • the thickness of the nylon 66 cell wall is preferably 1-3 mils.
  • the bags are then placed on racks or trays and placed into a large reaction chamber 8, which at various times functions as either an oven or as a cooling chamber, and in which a batch of mixture- filled bags 7 is polymerized.
  • the dimensions of the bags 7, the racks in which the bags are held, and the reaction chamber 8 have been designed to provide relatively high surface area of the bags.
  • the bags 7 are exposed to the ambient temperature within the reaction chamber 8, and the temperatures of the polymerizing mixture within each bag are kept very near to the ambient temperature within the reaction chamber 8 during either heating or cooling.
  • the reaction chamber 8 is provided with a conventional heating system 9, a conventional cooling system 10, and a conventional temperature control system 11 for establishing and maintaining a desired temperature at desired times within the reaction chamber 8.
  • the temperature control system 11 is a conventional microprocessor control system which maintains a deviation of ⁇ 0.5'C from a programmed temperature.
  • step 3 requires the addition of heat to maintain the polymerizing mixture in the bags at the desired temperatures for the desired times as set forth in Tables I-III. Also, in step 4, additional heat is required to push the polymerization to a high conversion and, regarding step 5, even more additional heat is added to push the polymerization reaction to extremely high conversion.
  • 2,5-dimethyl-2,5-di(t-butylperoxy) hexane was used as the high temperature initiator to aid in driving the polymerization to a high percentage of conversion
  • n-dodecyl mercaptan was used as a chain transfer agent.
  • Table IV shows the ingredients used in 1-5, and their specific weights.
  • the Table IV weights are the weights of the starting materials; all weights are in grams.
  • both a secondary initiator that is a high temperature initiator with a 10 hour half-life at greater than 100 * C
  • a mercaptan are used in the polymerization.
  • the purpose of adding the second initiator to the system is to drive the reaction to an extremely high conversion during the bulk polymerization.
  • Extremely high conversion percentage refers to the polymerization of the present invention in which over 98 percent of the monomer ingredients are converted to copolymer. In most conventional polymerization processes, the conversion rates are not as high because conventional processes usually have undesirable side reactions occurring, and these reactions cause branching at high conversion. Through the use of chain transfer agents, such as mercaptans, the bulk polymerization process of the present invention controls the branching and chain length so that extremely high conversion rates are facilitated.
  • One of the advantages of the bulk polymerization, high conversion polymerization of the present invention is that extremely clear and clean copolymers may thereby be produced.
  • contamination usually refers to particulate matter contained within the copolymer mixture, and in.this context refers both to the size of the particles contained as well as the number of particles.
  • conventional polymerization processes often produce relatively contaminated copolymers due to the transferring of unreacted monomer back into the reaction vessel for further polymerization, whereas the bulk polymerization process of the present invention avoids such a transfer.
  • the bulk polymerization process of the present invention employs a 0.2 micron filter to thus remove any particulate matter having a diameter equal to or greater than 0.2 micron and produce finished polymers free of larger particles.
  • the bulk polymerization process of the present invention as shown in Figure 1, avoids prolonged contact with air and the attendant particulate impurities contained therein, through use of closed systems, vacuum purges, and the aforementioned filter.
  • reaction temperature In a step-by-step increase of reaction temperature during this latter stage of polymerization, the slowing of the rate of propagation due to increased polymerization will be partially balanced by the increasing temperature, but not to the extent existing in the pre-Tromsdorff condition. Also, by increasing the reaction temperature and adding a secondary initiator, the conversion can be pushed to an extremely high conversion of greater than 80 percent.
  • the reaction is finished after six hours at 135°C in the fifth stage of polymerization. During this stage, that is, during the six hours at 135 * C, the residual monomers reach a minimum value of approximately one percent. Both the secondary initiator and the programmed time-temperature sequence promote the mobility of the unreacted monomer and chain radicals so that it is copoly erized even in a high viscosity environment.
  • the major purpose of adding the chain transfer agent in the bulk polymerization system is to shorten the chain length of all of the macromolecules and to provide for a reasonably narrow molecular weight distribution (MWD) . Also, because radicals with smaller chain lengths are not apt to become heavily entangled with neighboring molecules, the mobility of the shorter radicals will not change as much as those of the longer radicals. This relatively decreased mobility enhances uniformity of polymerization and is. thus desirable in the present invention. It has been discovered that the addition of mercaptan(s) or amines, organic sulfur compounds such as carbon disulfide, carbon tetrachloride and other known chain transfer agents, may be used. Mercaptans, however, are preferred.
  • the copolymers of the present invention may be 5 characterized in terms of residual monomer measurement, molecular weight, polydispersity, monomer composition, and glass transition temperature.
  • Residual Monomer 0 The residual monomer present in the copolymers of the present invention. Examples 1-5, was determined by a gas chromatography (GC) method. The purpose of the determination of residual monomers was to make sure that all of the polymers from the extremely high 5 conversion polymerization reaction were essentially
  • a modified GC injector was built and used to determine the residual monomer content.
  • the GC injector is a conventional injector, modified to include glass wool, placed inside of the injector liner 0 as described in ["reference A"].
  • the glass wool insert functions to block or filter solid polymers from the solution, so that the liquid phase, i.e.. the monomer, solvent, etc., passes into the column.
  • the liquid phase i.e.. the monomer, solvent, etc.
  • Table V presents the results of residual monomer measurements for Examples 1-5, previously described. 0 These data indicate that the Examples 1-5 copolymers of the present invention have been forced to an extremely high conversion. The low percentage of residual monomers typically does not have any significant influence on final physical properties in regard to the 5 end use of the acrylic polymer. The residual monomers in Examples 1-5 are shown in Table V below.
  • the molecular weights of the copolymers can also be controlled or adjusted by the amount of chain transfer agents used.
  • the chain transfer constant of each chain transfer agent, _ mercaptan is a parameter to be considered when adjusting the molecular weight of the final product, and the determination of how much mercaptan to be used is in accordance with known principles.
  • Examples 1-5 were determined through gel permeation chromatography (GPC) ; the results are set forth in Table VI. These data indicate that the molecular weights of all of Examples 1-5 are relatively close to each other. Table VI also shows the polydispersities of Examples 1-5 copolymers. Polydispersity refers to the ratio of Mw to Mn, i.e. *, the breadth of the molecular weight distribution. For purposes of this invention Mw is defined as the weight- average molecular weight, and Mn is the number-average molecular weight. Table VI
  • the operating conditions of the gel permeation chromatography unit are shown in Table VII. All of the measurements for molecular weight were carried out at 23 * C; the polymer concentration was 0.005 g/ml and Perkin-Elmer software (GPC-5) was used for the calculation and data analysis. The universal calibration was based on polystyrene standards. The Table VII data are shown below.
  • the integral curve of -0CH 3 is proportional to three times the number of protons of MMA monomer in the chain
  • the integral curve associated with the -NH proton is proportional to the number of protons of MI monomer in the chain.
  • Proton-NMR spectra were obtained from a Bruker WM-500 spectrometer equipped with a 32-FT-100 pulse NMR computer system.
  • the instrument conditions used in obtaining the data were: 500 MHZ spectrum width; 10 second acquisition time; 10 second delay time between pulse sequences; 20 microsecond pulse widths; and a 45° flip angle. All samples were dissolved in CDC£3 to give a concentration of 0.032g/ml, and then analyzed in 10mm ID sample tubes.
  • polycarbonates have relatively high glass transition temperatures; however, their cost is relatively high and their weatherability is relatively poor in comparison to both conventional acrylic polymers and to the acrylic copolymers of the present invention.
  • Example 6 Another copolymer of the present invention, Example 6 was prepared in sufficient quantity to be tested for various physical properties.
  • the Example 6 copolymer was made from the following ingredient mixture:
  • Tinuvin-PTM (from Ciba-Geigy) 0.569
  • the ingredient mixture was prepared as described above and with a time-temperature sequence as follows:
  • Tinuvin-PTM was added to improve ultraviolet protection because it is a known UV radiation absorber: Also, indigo toner is a known blue toner added to modify the color characteristics of the finished product.
  • Example 6 copolymer A number of samples of the Example 6 copolymer were made and tested in accordance with test method ASTM D-638 at 0.20 inches/minute and at room temperature.
  • the following Table X presents the test data on maximum load, tensile strength, modulus and elongation.
  • Example 6 copolymer Two samples of the Example 6 copolymer were also tested for compressive strength and modulus in accordance with ASTM D-648, using a heating rate of 2.0
  • Sample 1 had a width of
  • sample 2 had a width of 0.500 inch.
  • Each of the Examples 7-9 ingredient mix also contained 0.06g lauryl peroxide, 0.33g 2,5-dimethyl- 2,5-di(t-butylperoxy)hexane, 0.331 g n-dodecyl mercaptan, 0.027g Tinuvin-PTM, 0.417g stearyl alcohol, and 0.013g indigo toner.
  • the Examples 8-9 finished polymers were clear and the Example 7 polymer was yellow.
  • the polymerization cycle used was: 63 * C to the 8th hour,, then 75 * C for 3 hours, then 115 * C for 4 hours, and then 135 * C for 6 hours.
  • the measured onset Tg was 132.5'C.
  • the polymerization cycle used was: 63"C to the 8th hour, then 75 * C for 3 hours, then
  • the polymerization cycle used was: 63 * C to the 8th hour, then 75"C for 3 hours, then 115"C for 4 hours, and then 135 * C for 6 hours.
  • Example 10 formulation is preferable, in light of the relatively high Tg. It is also noted that although MMA/MI is the preferred copolymer in terms of clarity, the lack of availability of MI in commercially competitive quantities and prices at present will limit its commercial uses. On the other hand, N-cyclohexylmaleimide is available at commercially useful prices and quantities, and is thus an acceptable compound of the present invention, even though it lacks the clarity of the preferred maleimide copolymer.
  • Tinuvin-PTM from Ciba-Geigy
  • Stearyl alcohol internal lubricant
  • Indigo toner 0.3ml
  • Tinuvin-PTM (from Ciba-Geigy) 0.06g
  • Example 15 copolymer was yellow and had an onset Tg of 126°C.
  • the Example 16 copolymer was slightly yellow and had a Tg of 129°C.
  • the Example 17 copolymer was clear and had a Tg of 120°C.
  • a production scale copolymer of the present invention was also made with the following ingredient mixture:
  • the polymerization cycle was as follows: 63°C to the 8th hour, then 75 ⁇ C for 3 hours, then 115 q C for 4 hours, and then 140°C for 6 hours.
  • the copolymer was yellow and had an onset Tg of 130°, with a midpoint Tg of 135°C.
  • the M thread was 45,000, the M consult was 95,000 and the P d was 2.1.
  • the copolymer had a specific gravity of 1.194.
  • the copolymers of the present invention are prepared by a bulk polymerization process as described, they do not contain residual emulsifiers, solvents or dispersion agents as would copolymers produced by other polymerization techniques. These impurities operate to lower Tg's and to degrade the clarity of the resulting copolymers.
  • the copolymers of the present invention are substantially emulsifier free, solvent free and dispersion agent free. They also exhibit extremely good clarity, absences of particulate and have higher Tg's than identical copolymers produced by other methods.
  • the bulk polymerization process of the present invention is generally less costly than conventional extrusion technology.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
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Abstract

Copolymère de méthacrylate-maléimide résistant aux températures élevées qui possède au moins 90 % en poids d'un monomère de méthacrylate de méthyle et jusqu'à environ 10 % en poids d'un monomère de maléimide pour former un copolymère clair et résistant aux intempéries ayant des températures de transition vitreuse situées entre environ 105 °C et environ 131 °C, et méthode de fabrication desdits copolymères grâce à un procédé de polymérisation en masse à taux de conversion extrêmement élevés.
PCT/US1991/005641 1989-03-13 1991-08-08 Acryliques resistant a des temperatures elevees WO1993003076A1 (fr)

Priority Applications (8)

Application Number Priority Date Filing Date Title
US07/322,615 US5073615A (en) 1989-03-13 1989-03-13 High temperature heat resistant acrylics
JP4502799A JPH06506962A (ja) 1989-03-13 1991-08-08 高温耐熱性アクリリクス
BR919107027A BR9107027A (pt) 1991-08-08 1991-08-08 Acrilicos resistentes ao calor em temperatura elevada
CA002093636A CA2093636A1 (fr) 1989-03-13 1991-08-08 Acryliques resistant aux hautes temperatures
EP19920901995 EP0557457A4 (en) 1989-03-13 1991-08-08 High temperature heat resistant acrylics
PCT/US1991/005641 WO1993003076A1 (fr) 1989-03-13 1991-08-08 Acryliques resistant a des temperatures elevees
US07/931,763 US5319043A (en) 1989-03-13 1992-08-18 High temperature heat resistant acrylics method of manufacture
US08/020,294 US5328962A (en) 1989-03-13 1993-02-19 High heat acrylics

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US07/322,615 US5073615A (en) 1989-03-13 1989-03-13 High temperature heat resistant acrylics
CA002093636A CA2093636A1 (fr) 1989-03-13 1991-08-08 Acryliques resistant aux hautes temperatures
PCT/US1991/005641 WO1993003076A1 (fr) 1989-03-13 1991-08-08 Acryliques resistant a des temperatures elevees

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Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0560620A1 (fr) * 1992-03-12 1993-09-15 Toray Industries, Inc. Polymères à groupes maléimide et lentilles de contact fabriquées à partir de ces polymères
FR2726827A1 (fr) * 1994-11-10 1996-05-15 Roehm Gmbh Procede de preparation de copolymeres de methacrylate d'alkyle
US5998556A (en) * 1995-09-27 1999-12-07 Nippon Shokubai Co., Ltd. Raw material used for producing heat-resistant resins, heat-resistant resins, and process for producing heat-resistant resins
EP1108731A2 (fr) * 1999-12-13 2001-06-20 Nippon Shokubai Co., Ltd. Résine transparente résistant à la chaleur et son procédé de préparation
KR101342713B1 (ko) * 2013-04-19 2013-12-18 (주)비피케미칼 수분산성 아크릴계 에멀젼
EP2670388A4 (fr) * 2011-01-31 2016-09-07 Key Medical Technologies Inc Procédé de fabrication de dispositifs ophtalmiques et de composants de ceux-ci à partir de polymères acryliques hydrophobes (ah) à scintillements réduits ou supprimés
US9920148B2 (en) 2012-10-19 2018-03-20 Asahi Kasei Chemicals Corporation Vehicle part cover including methacrylic-based resin
KR20180063968A (ko) * 2016-12-02 2018-06-14 주식회사 효성 아크릴 필름
KR20180063969A (ko) * 2016-12-02 2018-06-14 주식회사 효성 코팅 아크릴 필름
KR20180079614A (ko) * 2016-12-30 2018-07-11 주식회사 효성 내가열(耐加熱) 내백화(耐白化) 필름
KR20180079613A (ko) * 2016-12-30 2018-07-11 주식회사 효성 내가열(耐加熱) 내백화(耐白化) 필름
KR20180079616A (ko) * 2016-12-30 2018-07-11 주식회사 효성 내응력(耐應力) 내백화(耐白化) 필름
KR20180079615A (ko) * 2016-12-30 2018-07-11 주식회사 효성 내응력(耐應力) 내백화(耐白化) 필름
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KR101894811B1 (ko) * 2016-12-02 2018-10-19 주식회사 효성 코팅 아크릴 필름
KR101928871B1 (ko) 2018-09-17 2018-12-13 주식회사 효성 Ips lcd 패널
KR101928862B1 (ko) * 2016-12-02 2018-12-14 효성화학 주식회사 아크릴 필름
KR101928860B1 (ko) * 2016-12-02 2018-12-14 효성화학 주식회사 아크릴 필름
KR20180134784A (ko) * 2018-09-28 2018-12-19 효성화학 주식회사 내응력(耐應力) 내백화(耐白化) 필름
KR101936669B1 (ko) 2018-09-28 2019-01-09 효성화학 주식회사 내응력(耐應力) 내백화(耐白化) 필름
KR101936672B1 (ko) 2018-09-28 2019-01-09 효성화학 주식회사 내가열(耐加熱) 내백화(耐白化) 필름
KR101936667B1 (ko) 2018-09-28 2019-01-09 효성화학 주식회사 내가열(耐加熱) 내백화(耐白化) 필름
KR101936702B1 (ko) * 2016-12-02 2019-01-10 효성화학 주식회사 코팅 아크릴 필름
KR101947484B1 (ko) * 2016-12-02 2019-02-14 효성화학 주식회사 코팅 아크릴 필름
CN111718439A (zh) * 2020-06-19 2020-09-29 宁波南大光电材料有限公司 甲基丙烯酸树脂及其制备方法和应用

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EP0560620A1 (fr) * 1992-03-12 1993-09-15 Toray Industries, Inc. Polymères à groupes maléimide et lentilles de contact fabriquées à partir de ces polymères
FR2726827A1 (fr) * 1994-11-10 1996-05-15 Roehm Gmbh Procede de preparation de copolymeres de methacrylate d'alkyle
US5998556A (en) * 1995-09-27 1999-12-07 Nippon Shokubai Co., Ltd. Raw material used for producing heat-resistant resins, heat-resistant resins, and process for producing heat-resistant resins
EP1108731A2 (fr) * 1999-12-13 2001-06-20 Nippon Shokubai Co., Ltd. Résine transparente résistant à la chaleur et son procédé de préparation
EP1108731A3 (fr) * 1999-12-13 2001-09-05 Nippon Shokubai Co., Ltd. Résine transparente résistant à la chaleur et son procédé de préparation
US6417306B1 (en) 1999-12-13 2002-07-09 Nippon Shokubai Co., Ltd, Transparent heat-resistant resin and production process therefor
KR100452045B1 (ko) * 1999-12-13 2004-10-08 니폰 쇼쿠바이 컴파니 리미티드 투명성 내열수지 및 이의 제조방법
EP2670388A4 (fr) * 2011-01-31 2016-09-07 Key Medical Technologies Inc Procédé de fabrication de dispositifs ophtalmiques et de composants de ceux-ci à partir de polymères acryliques hydrophobes (ah) à scintillements réduits ou supprimés
US9920148B2 (en) 2012-10-19 2018-03-20 Asahi Kasei Chemicals Corporation Vehicle part cover including methacrylic-based resin
KR101342713B1 (ko) * 2013-04-19 2013-12-18 (주)비피케미칼 수분산성 아크릴계 에멀젼
KR101928860B1 (ko) * 2016-12-02 2018-12-14 효성화학 주식회사 아크릴 필름
KR101936702B1 (ko) * 2016-12-02 2019-01-10 효성화학 주식회사 코팅 아크릴 필름
KR101956614B1 (ko) * 2016-12-02 2019-06-28 효성화학 주식회사 아크릴 필름
KR101947484B1 (ko) * 2016-12-02 2019-02-14 효성화학 주식회사 코팅 아크릴 필름
KR20180063969A (ko) * 2016-12-02 2018-06-14 주식회사 효성 코팅 아크릴 필름
KR20180063968A (ko) * 2016-12-02 2018-06-14 주식회사 효성 아크릴 필름
KR101928862B1 (ko) * 2016-12-02 2018-12-14 효성화학 주식회사 아크릴 필름
KR101894812B1 (ko) * 2016-12-02 2018-09-05 주식회사 효성 코팅 아크릴 필름
KR101894811B1 (ko) * 2016-12-02 2018-10-19 주식회사 효성 코팅 아크릴 필름
KR20180079490A (ko) * 2016-12-30 2018-07-11 주식회사 효성 Ips lcd 패널
KR20180079615A (ko) * 2016-12-30 2018-07-11 주식회사 효성 내응력(耐應力) 내백화(耐白化) 필름
KR20180079616A (ko) * 2016-12-30 2018-07-11 주식회사 효성 내응력(耐應力) 내백화(耐白化) 필름
KR20180079613A (ko) * 2016-12-30 2018-07-11 주식회사 효성 내가열(耐加熱) 내백화(耐白化) 필름
KR20180079614A (ko) * 2016-12-30 2018-07-11 주식회사 효성 내가열(耐加熱) 내백화(耐白化) 필름
KR101928871B1 (ko) 2018-09-17 2018-12-13 주식회사 효성 Ips lcd 패널
KR20180134784A (ko) * 2018-09-28 2018-12-19 효성화학 주식회사 내응력(耐應力) 내백화(耐白化) 필름
KR101936669B1 (ko) 2018-09-28 2019-01-09 효성화학 주식회사 내응력(耐應力) 내백화(耐白化) 필름
KR101936672B1 (ko) 2018-09-28 2019-01-09 효성화학 주식회사 내가열(耐加熱) 내백화(耐白化) 필름
KR101936667B1 (ko) 2018-09-28 2019-01-09 효성화학 주식회사 내가열(耐加熱) 내백화(耐白化) 필름
KR101939324B1 (ko) 2018-09-28 2019-01-16 효성화학 주식회사 내응력(耐應力) 내백화(耐白化) 필름
CN111718439A (zh) * 2020-06-19 2020-09-29 宁波南大光电材料有限公司 甲基丙烯酸树脂及其制备方法和应用

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