CN1488670A - Methacrylic acid resin moulded product and its production method and resin compositon for producing said product - Google Patents
Methacrylic acid resin moulded product and its production method and resin compositon for producing said product Download PDFInfo
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- CN1488670A CN1488670A CNA03158036XA CN03158036A CN1488670A CN 1488670 A CN1488670 A CN 1488670A CN A03158036X A CNA03158036X A CN A03158036XA CN 03158036 A CN03158036 A CN 03158036A CN 1488670 A CN1488670 A CN 1488670A
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- peroxide
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- 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
- C08F20/00—Homopolymers and 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
- C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
- C08F20/10—Esters
- C08F20/12—Esters of monohydric alcohols or phenols
- C08F20/14—Methyl esters, e.g. methyl (meth)acrylate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C39/00—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor
- B29C39/003—Shaping by casting, i.e. introducing the moulding material into a mould or between confining surfaces without significant moulding pressure; Apparatus therefor characterised by the choice of material
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- 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
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/10—Homopolymers or copolymers of methacrylic acid esters
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
- Polymerization Catalysts (AREA)
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
To provide a method which makes it possible to manufacture a cast molded article of an impact-resistant methacrylate resin, having sufficient impact resistance, a low residual monomer content, and higher transparency. A composition is used which contains a monomer comprising mainly methyl methacrylate, a methacrylate resin comprising mainly methyl methacrylate units, (multilayer) elastic material particles, a first organic peroxide comprising a monofunctional organic peroxide having a 10-hr half-life temperature of 60[deg.]C or lower, a second organic peroxide comprising a monofunctional organic peroxide having a 10-hr half-life temperature of above 60[deg.]C to 80[deg.]C, and a third organic peroxide comprising a monofunctional organic peroxide having a 10-hr half-life temperature of above 80[deg.]C. The composition is polymerized by keeping it in a polymerization cell at a temperature, for example, lower than the 10-hr half-life temperature of the first organic peroxide by at least 10[deg.]C, and then raising the temperature to a temperature higher than the 10-hr half-life temperature of the third organic peroxide by at least 10[deg.]C. The obtained molded article is excellent in transparency and the like.
Description
Technical field
The present invention relates to a kind of shock resistance methacrylic resin moulded parts and production method thereof and make the resin combination of this moulded parts.
Background technology
Contain elastic granule and can be used to association areas such as insulating board on membrane and the highway by casting polymerization synthetic methacrylic resin casting article.Japanese patent application postpones publication number JP-A-8-151498 and discloses a kind of method by a kind of composition production shock resistance of polymerization methacrylic resin casting article in polymeric pool, and described composition comprises that containing methyl methacrylate monomer is methacrylic resin, elastic granule and the polymerization starter that formant constitutes as the monomer of main ingredient, by methyl methacrylate.This patent documentation also discloses polymerization starter can be organo-peroxide, azo-compound or their analogue.
Usually, shock resistance methacrylic resin casting article needs enough shock resistances, the monomer of residual minute quantity and have enough transparencies in the goods.
Yet, contain relatively large residual monomer in the shock resistance methacrylic resin casting article by traditional technology production, simultaneously also not really transparent.
Summary of the invention
One of purpose of the present invention provides the method that contains the minute quantity residual monomer in a kind of article of manufacture and have the shock resistance methacrylic resin casting article of enough high-clarity.Inventor's result of study shows: have been found that and contain the minute quantity residual monomer, have enough high impact properties and the shock resistance methacrylic resin moulded parts of enhancing the transparency greatly and can contain the resin combination of multiple simple function organo-peroxide with 10 hours different half life temperatures by use production obtains as polymerization starter.
The invention provides a kind of resin combination, comprise:
At least a monomer that contains methyl methacrylate monomer;
Methacrylic resin with methyl methacrylate units;
Elastic granule;
Half life temperature was less than or equal to 60 ℃ the first simple function organo-peroxide in 10 hours;
10 hours half life temperatures are greater than 60 ℃ and be less than or equal to 80 ℃ the second simple function organo-peroxide;
With 10 hours half life temperatures the 3rd simple function organo-peroxide greater than 80 ℃.
The present invention also provides a kind of methacrylic resin casting article and production method thereof that adopts above-mentioned resin combination to obtain.
Embodiment
Resin combination of the present invention comprises:
At least a monomer that contains methyl methacrylate monomer;
Methacrylic resin with methyl methacrylate units;
Elastic granule;
Half life temperature was less than or equal to 60 ℃ the first simple function organo-peroxide in 10 hours;
10 hours half life temperatures are greater than 60 ℃ and be less than or equal to 80 ℃ the second simple function organo-peroxide;
With 10 hours half life temperatures the 3rd simple function organo-peroxide greater than 80 ℃.
The monomer that uses among the present invention comprises methyl methacrylate monomer.Preferably, to comprise methyl methacrylate be major ingredient to monomer; More preferably, the methyl methacrylate monomer that comprises at least 50 weight %.
This monomer (one or more) both can be a methyl methacrylate monomer itself, also can be methyl methacrylate monomer and the mixture that can form with the monomer of its copolymerization.Can for example comprise with the monomeric example of methyl methacrylate monomer copolymerization: esters of acrylic acid such as methyl acrylate, ethyl propenoate and ethyl acrylate; Methyl acrylic ester such as Jia Jibingxisuanyizhi, n-BMA, Propenoic acid, 2-methyl, isobutyl ester and methacrylic acid-2-ethylhexyl; Methacrylic acid; Maleic anhydride; Vinylbenzene; The cyclohexyl maleimide; Vinyl cyanide etc.Notice that methyl acrylic ester does not comprise methyl methacrylate.These copolymerisable monomers can add separately, also can add by two or more mixed forms.As mentioned above, if use the mixture that contains copolymerisable monomer, so, methyl methacrylate monomer preferably accounts for 50 weight % or more of mixture.
Methyl methacrylate and the oligopolymer that can form with the monomer of its copolymerization as dipolymer, trimer etc.
The methacrylic resin that uses among the present invention is the methacrylic resin with methyl methacrylate units, and preferably, methyl methacrylate units is a major ingredient in the methacrylic resin; More preferably, methyl methacrylate units accounts for 50 weight % or more in the methacrylic resin.
This methacrylic resin can be the homopolymer of methyl methacrylate, also can be methyl methacrylate and can with the monomeric multipolymer of its copolymerization.Can comprise and the identical monomer of the above-mentioned monomer of enumerating with the monomeric example that methyl methacrylate copolymer forms multipolymer, described monomer can be included in contain methyl methacrylate monomer and can with the monomer of methyl methacrylate copolymer in.If use multipolymer as methacrylic resin, so, preferably contain 50 weight % or more methyl methacrylate units in the multipolymer.Preferably, the viscosity-average molecular weight of methacrylic resin is more than or equal to about 10000 and be less than or equal to about 300000.
The elastic granule that uses among the present invention can be the elastic granule with elastomerics single layer structure.In addition, elastic granule also can be the elastic granule with multilayered structure, and for example, double-deck elastic granule: with the elastomerics is core, coats the methacrylic resin layer around it; The elastic granule of three-decker: with the methacrylic resin is core, and the middle layer of coated elastomer around it, middle layer coat the skin of methacrylic resin on every side.The diameter of elastic granule can be more than or equal to 0.1 μ m and is less than or equal to 1 μ m, preferably, and more than or equal to 0.2 μ m and be less than or equal to 0.8 μ m.If the diameter of elastic granule is less than 0.1 μ m, shock resistance reduces; If the diameter of elastic granule is during greater than 1 μ m, transparency reduces.Because the excellent transparency of the shock resistance methacrylic resin casting article that forms, the elastic granule of therefore preferred use multilayered structure is the elastic granule of three-decker particularly.
This elastic granule as the shock resistance methacrylic resin is that commerce can get, for example: " SumipexHT01X " (Sumitomo chemistry limited-liability company sells), " Oroglas DR " (sale of Sumitomo-Haas company) etc.The elastic granule that this commerce can get is dispersed in the methacrylic resin.
The weight ratio of the methacrylic resin/elastic granule in the resin combination of the present invention (being the weight ratio of methacrylic resin and elastic granule) is preferably in 3/7～7/3 scope.Gross weight umber in monomer, methacrylic resin and elastic granule is 100 parts, and the total amount of methacrylic resin and elastic granule is preferably more than or equals 10 weight parts and be less than or equal to 40 weight parts.When the total amount of methacrylic resin and elastic granule during less than 10 weight parts, the shock resistance deficiency of made moulded parts; And when total amount during greater than 40 weight parts, the viscosity of this resin combination is higher, and it is difficult to be filled in the polymeric pool.
Resin combination of the present invention contain as 10 hours half life temperatures of polymerization starter be less than or equal to 60 ℃ the first simple function organo-peroxide, 10 hours half life temperatures greater than 60 ℃ and be less than or equal to 80 ℃ the second simple function organo-peroxide and 10 hours half life temperatures greater than 80 ℃ the 3rd simple function organo-peroxide.
Each organo-peroxide among the present invention all is the organic compound that contains the key that following formula represents in the molecule:
-O-O-
Organo-peroxide produces free radical by the decomposition of this key.10 hours of the present invention half life temperature (T) be that organo-peroxide decomposed the temperature of half in 10 hours when independent heating organo-peroxide.The Arrhenius equation formula of the one-level decomposition reaction of the organo-peroxide that this temperature can be measured by need obtains, this equation can obtain by the variable quantity that the quantity of degradation production is passed in time, wherein organo-peroxide is dissolved in the inert solvent such as benzene, and the solution that adds thermosetting then under steady temperature produces degradation production.
An aforesaid key is arranged (O-O-) in the simple function organo-peroxide molecule of the present invention.(multifunctional organo-peroxide O-O-), during as di-tert-butyl peroxide trimethyladipic acid ester, the residual monomer quantity in the made moulded parts will increase to contain two or more keys in using molecule.
The example of the first simple function organo-peroxide for example comprises: the own ester of peroxidation neodecanoic acid uncle (T (10 hours half life temperatures)=45 ℃), peroxy dicarbonate two (methoxyl group fourth) ester (T=46 ℃), new peroxide tert-butyl caprate (T=46 ℃), the own ester of peroxidation PIVALIC ACID CRUDE (25) uncle (T=53 ℃), the peroxidation PIVALIC ACID CRUDE (25) tert-butyl ester (T=55 ℃), peroxidation (3,5, the 5-trimethyl acetyl) (T=59 ℃) etc.For the ease of operation, preferably use 10 hours half life temperatures more than or equal to 40 ℃ the first simple function organo-peroxide; More preferably, 10 hours half life temperatures are more than or equal to 50 ℃.
The example of the second simple function organo-peroxide for example comprises: peroxidation decoyl (T=62 ℃), lauroyl peroxide (T=62 ℃), stearoyl (T=62 ℃), peroxidation-2 ethyl hexanoic acid 1,1,3,3-tetramethyl-butyl ester (T=66 ℃), succinyl peroxide (T=66 ℃), peroxidation-2 ethyl hexanoic acid 1-cyclohexyl-1-methyl ethyl ester (T=68 ℃), the peroxidation-own ester of 2 ethyl hexanoic acid uncle (T=70 ℃), peroxide-2-ethyl hexanoic acid tert-butyl (T=72 ℃), peroxidation tert-butyl isobutyrate (T=78 ℃) etc.
The example of the 3rd simple function organo-peroxide for example comprises: the own ester of peroxy isopropyl base one carbonic acid uncle (T=95 ℃), t-butyl peroxy toxilic acid (T=96 ℃), peroxidation-3,5, the 5-tri-methyl hexanoic acid tert-butyl ester (T=97 ℃), the peroxidation lauric acid tert-butyl ester (T=98 ℃), the peroxy isopropyl base one carbonic acid tert-butyl ester (T=99 ℃), peroxide (2-ethylhexyl) carbonic acid tert-butyl ester (T=99 ℃), the own ester of peroxidation phenylformic acid uncle (T=99 ℃), peroxide acetic acid butyl ester (T=102 ℃), peroxidized t-butyl perbenzoate (T=104 ℃), dicumyl peroxide (T=119 ℃), tertiary butyl cumyl peroxide (T=120 ℃).Because the top temperature during polymerization can be lower, preferably uses 10 hours half life temperatures to be less than or equal to 110 ℃ the 3rd simple function organo-peroxide.
Since can obtain the more excellent shock resistance methacrylic resin casting article of transparency, therefore, 10 hours half life temperature (T of the first simple function organo-peroxide
1) and 10 hours half life temperature (T of the second simple function organo-peroxide
2) between difference (Δ T
12) be preferably greater than or equal 10 ℃; More preferably greater than or equal 13 ℃, and can be less than or equal to 30 ℃.Similarly, owing to can obtain the more excellent shock resistance methacrylic resin casting article of transparency, 10 hours half life temperature (T of the second simple function organo-peroxide
2) and 10 hours half life temperature (T of the 3rd simple function organo-peroxide
3) between difference (Δ T
23) be preferably greater than or equal 10 ℃; More preferably greater than or equal 18 ℃, and preferably be less than or equal to 35 ℃.
The weight ratio of the first simple function organo-peroxide/second simple function organo-peroxide in the resin combination of the present invention (i.e. the weight ratio of the first simple function organo-peroxide and the second simple function organo-peroxide) can be in 3/7～7/3 scope, preferably in 4/6～6/4 scope.Similarly, the total amount of the first and second simple function organo-peroxides in the resin combination of the present invention and the weight ratio of the 3rd simple function organo-peroxide can be in 3/7～7/3 scopes, preferably in 4/6～6/4 scope.By the monomer weight umber that comprises methyl methacrylate monomer is 100 parts, and the total amount of first, second and the 3rd simple function organo-peroxide can be in the scope of 0.05～0.5 weight part.
Can use respectively first, second and the 3rd simple function organo-peroxide through solvent cut.This inert solvent can reasonably be selected according to the type of this simple function organo-peroxide, and the example of inert solvent comprises saturated fatty varsol such as petroleum naphtha and mineral turpentine; Varsol such as benzene and toluene; Acetone; Cumene; Diphenylethane; Ethyl acetate etc.
Except monomer, methacrylic resin, elastic granule, the first simple function organo-peroxide, the second simple function organo-peroxide and the 3rd simple function organo-peroxide, resin combination of the present invention also can contain such as additives such as antioxidant, uv-absorbing agent, remover, dyestuffs according to the Application Areas of required shock resistance methacrylic resin moulded parts.
Can prepare by the above-mentioned resin combination of polymerization and to have enough shock resistances, the methacrylic resin moulded parts of residue minute quantity monomer and excellent transparency.
The present invention has no particular limits polymerization process, and that can enumerate has polymerization processs such as mass polymerization, casting polymerization.Hereinafter, described and in polymeric pool, realized the polymeric plastic casting polymerization method, but should not think limitation of the scope of the invention.
When carrying out polymerization in polymeric pool, employed polymeric pool is had no particular limits, any polymeric pool of using in the general plastic casting polymerization method all can be used for the present invention.Such as, obtain tabular methacrylic resin casting article, can use intermittence type polymerization pond that constitutes by two substrates that are parallel to each other or the continous way polymeric pool that constitutes by two continuous conveyors that are parallel to each other.
When using the intermittence type polymerization pond, described substrate can use glass substrate or metal substrate.These two substrates are provided with and constitute two walls of polymeric pool apart from each other, and four remaining walls are made of soft sealing material.Resin combination polymerization in this polymeric pool is promptly carried out polyreaction in the zone that is surrounded by these two substrates and soft sealing material.The spacing of two substrates can reasonably be selected according to the thickness of the tabular moulded parts that will make, and can be about 5～30mm.The substrate spacing can be regulated by the thickness that changes soft sealing material, can also push soft sealing material by the promotion two boards and regulate.
The polymerization of the resin combination that carries out in polymeric pool can be heated this polymeric pool and realize then by such as pour resin combination in polymeric pool.For instance, polymerization is by at 10 hours half life temperature (T than the first simple function organo-peroxide
1) low at least 5 ℃ temperature (as 30 ℃ or higher) insulation 10 hours or longer down, elevated temperature is to 10 hours half life temperature (T than the 3rd simple function organo-peroxide then
3) high at least 5 ℃ but be lower than as 140 ℃ and carry out.Polymerization temperature can progressively raise, and also can raise continuously, and preferably, polymerization temperature progressively raises.When polymerization temperature progressively raise, polymerization was preferably passed through at 10 hours half life temperature (T than the first simple function organo-peroxide
1) insulation 10 hours or longer under low at least 5 ℃ the temperature, then temperature maintenance at 10 hours half life temperature (T than the first simple function organo-peroxide
1) in low about 5 ℃～high about 10 ℃ scope, be incubated 1 hour or longer, again temperature maintenance at 10 hours half life temperature (T than the second simple function organo-peroxide
2) hang down in about 10 ℃～high about 10 ℃ scope, being incubated 1 hour or longer, last elevated temperature is to 10 hours half life temperature (T than the 3rd simple function organo-peroxide
3) high at least 5 ℃ carry out.For elevated temperature can use hot water, warm air or steam.
Decompose the generation free radical when the first simple function organo-peroxide in the resin combination, the second simple function organo-peroxide and the 3rd simple function organo-peroxide heat, cause the resin combination polymerization, form moulded parts of the present invention.
Finish in polymeric pool after the polyreaction, the dismounting polymeric pool is taken out shock resistance methacrylic resin casting article.The shock resistance methacrylic resin casting article that obtains by this way has enough shock resistances and fabulous transparency.Therefore, this moulded parts can be used as for example sheet material, the insulating board on the highway or the armour etc. of membrane.
According to the present invention, the shock resistance methacrylic resin casting article that can make residue minute quantity monomer, has enough high impact properties and excellent clarity.
Obviously, can change foregoing invention by variety of way.These variations are considered to drop within essence of the present invention and the scope, and all are that conspicuous these changes all fall within the scope of the appended claims to those skilled in the art.
The application number that on August 5th, 2002 submitted is whole disclosures of the Japanese patent application of No.2002-227032: specification sheets, claims, accompanying drawing and summary are incorporated herein by reference.
Embodiment
Describe the present invention in detail with reference to the following examples, but should not think limitation of the scope of the invention to these embodiment.
The residual monomer amount of moulded parts records in order to following method among each embodiment:
From each moulded parts, downcut sample (0.1g) respectively, be dissolved in 20cm
3Methylene dichloride in.In gained solution, adding 15mm
3Methyl iso-butyl ketone (MIBK) (as interior mark) after, the monomer component in the solution is measured quantitatively by gas chromatographic analysis.
The turbidity of moulded parts is used in the moulded parts of handling in 1 hour through 23 ℃ of constant temperature in the automatic heat regulator according to JIS K7136 and records.
But shellfish (Charpy) shock strength of moulded parts records with 1 type sample according to JIS K7111.
Embodiment 1
The preparation of resin combination
Methacrylic resin (13.5 weight parts that are copolymerized into methyl methacrylate (77.5 weight part), by 95 weight % methyl methacrylate units and 5 weight % methyl acrylate unit; Viscosity-average molecular weight is about 110000) and elastic granule (9 weight parts with three-decker; Particle diameter is 0.3 μ m) mixed 60 ℃ of following stirrings 2 hours that are incorporated in.After the cooling, in the gained mixture, add the peroxidation PIVALIC ACID CRUDE (25) tert-butyl ester (0.014 weight part; T (10 hours half life temperatures)=55 ℃) (concentration is 70 weight % to be dissolved in solution in the saturated fatty varsol; 0.02 peroxide-2-ethyl hexanoic acid tert-butyl (0.02 weight part weight part); Purity is more than or equal to 97 weight %; The pure product of about 0.02 weight part; T=72 ℃), the peroxy isopropyl base carbonic acid tert-butyl ester (0.03 weight part; T=99 ℃) (concentration is 75 weight % to be dissolved in solution in the varsol; 0.04 uv-absorbing agent (0.01 weight part weight part); Trade(brand)name " Sumisorb 200 "; Sumitomo chemistry limited-liability company sells), remover (0.05 weight part; Trade(brand)name " Sanseparer "; Sanyo chemical industry company limited sells).Behind the restir 1 hour, the mixture of gained obtains resin combination after 87kPa (pounds per square inch absolute (psia)) outgased 30 minutes down.Polymerization
The resin combination of above-mentioned preparation is injected in the polymeric pool of the sealing material formation of being made by two sheet glass (30cm * 30cm, thickness are 10mm) and soft polyvinyl chloride.Resin combination in the heated polymerizable pond also is incubated 16 hours under 46 ℃, further the temperature rise rate with 0.25 ℃/min is heated to 51 ℃, be incubated 4 hours down at 51 ℃, temperature rise rate with 0.45 ℃/min is heated to 60 ℃ again, be incubated 3 hours down at 60 ℃ again, temperature rise rate with 0.5 ℃/min is heated to 70 ℃ then, be incubated 3 hours down at 70 ℃ then, temperature rise rate with 0.5 ℃/min is heated to 85 ℃ then, be incubated 3 hours down at 85 ℃, temperature rise rate with 0.5 ℃/min is heated to 120 ℃ at last, is incubated 2 hours down at 120 ℃ again, and further is incubated 3 hours in 120 ℃～125 ℃ temperature range.Use circulating warm air beating stove to heat.After heat-processed finished, the composition of cooling gained was dismantled polymeric pool then, and it is (tabular to obtain the shock resistance methacrylic resin moulded parts that is polymerized by resin combination; 30cm * 30cm * 10mm (thickness)).Estimate
Downcut sample from the moulded parts of making, measure the residual monomer amount, turbidity of this moulded parts and but shellfish (Charpy) shock strength.The result is: the residual monomer amount is 0.9 weight %, and turbidity is 0.7%, and but shellfish (Charpy) shock strength is 36kJ/m
2Evaluation result sees Table 1.
Embodiment 2
Prepare tabular shock resistance methacrylic resin casting article by the mode identical with embodiment 1, different is at mixed methyl methyl acrylate, methacrylic resin, have the elastic granule of three-decker after, 60 ℃ of following agitating resin compositions 13 hours.The evaluation result of made moulded parts sees Table 1.
Comparative Examples 1
Prepare tabular shock resistance methacrylic resin casting article by the mode identical with embodiment 1, different is only to use 2 of 0.08 weight part, 2-Diisopropyl azodicarboxylate (azo-compound, T=65 ℃) replaces peroxidation PIVALIC ACID CRUDE (25) tert-butyl ester solution, peroxide-2-ethyl hexanoic acid tert-butyl solution and peroxy isopropyl base carbonic acid tert-butyl ester solution.The evaluation result of made moulded parts sees Table 1.
Comparative Examples 2
Prepare tabular shock resistance methacrylic resin moulded parts by the mode identical with embodiment 1, different is only to use 0.08 weight part (the pure product of about 0.08 weight part) peroxide-2-ethyl hexanoic acid tert-butyl (purity is more than or equal to 97 weight %) to replace peroxidation PIVALIC ACID CRUDE (25) tert-butyl ester solution, peroxide-2-ethyl hexanoic acid tert-butyl solution and peroxy isopropyl base carbonic acid tert-butyl ester solution.The evaluation result of made moulded parts sees Table 1.
Comparative Examples 3
Prepare tabular shock resistance methacrylic resin moulded parts by the mode identical with embodiment 1, different 2 of 0.02 parts by weight that are to use, 2 '-azo two (2, the 4-methyl pentane nitrile) (azo-compound, T=51 ℃) replacement peroxidation PIVALIC ACID CRUDE (25) tert-butyl ester solution.The evaluation result of made moulded parts sees Table 1.
Comparative Examples 4
Prepare tabular shock resistance methacrylic resin moulded parts by the mode identical with embodiment 1, the solution (concentration 50 weight %) that different is only uses the di-tert-butyl peroxide trimethyladipic acid ester (multifunctional organo-peroxide) of 0.23 weight part (the pure product of about 0.115 weight part) to be dissolved in isoparaffin replaces peroxidation PIVALIC ACID CRUDE (25) tert-butyl ester solution, peroxide-2-ethyl hexanoic acid tert-butyl solution and peroxy isopropyl base one carbonic acid tert-butyl ester solution.The evaluation result of made moulded parts sees Table 1.
Table 1
| 10 hours half life temperatures | Embodiment 1 | Embodiment 2 | Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 | Comparative Examples 4 | |
| The peroxidation PIVALIC ACID CRUDE (25) tert-butyl ester | 55℃ | 0.014 | ?0.014 | ?- | ?- | ?- | ?- |
| Peroxide-2-ethyl hexanoic acid tert-butyl | 72℃ | 0.02 | ?0.02 | ?- | ?0.08 | ?0.02 | ?- |
| Peroxy isopropyl base-carbonic acid the tert-butyl ester | 99℃ | 0.03 | ?0.03 | ?- | ?- | ?0.03 | ?- |
| Di-tert-butyl peroxide trimethyladipic acid ester (multifunctional organo-peroxide) | - | ?- | ?- | ?- | ?- | ?0.115 | |
| 2, the 2-Diisopropyl azodicarboxylate | 65℃ | - | ?- | ?0.08 | ?- | ?- | ?- |
| 2,2 ' azo two (2, the 4-methyl pentane nitrile) | 51℃ | - | ?- | ?- | ?- | ?0.02 | ?- |
| Residual monomer amount (%) | 0.9 | ?0.8 | ?1.5 | ?2.7 | ?0.9 | ?1.2 | |
| Turbidity (%) | 0.7 | ?0.9 | ?1.4 | ?5.2 | ?3.7 | ?0.5 | |
| Charpy impact intensity (kJ/m 2) | 36 | ?37 | ?48 | ?35 | ?24 | ?45 | |
Claims (15)
1. resin combination comprises:
At least a monomer that contains methyl methacrylate monomer;
Methacrylic resin with methyl methacrylate units;
Elastic granule;
Half life temperature was less than or equal to 60 ℃ the first simple function organo-peroxide in 10 hours;
10 hours half life temperatures are greater than 60 ℃ and be less than or equal to 80 ℃ the second simple function organo-peroxide;
With 10 hours half life temperatures the 3rd simple function organo-peroxide greater than 80 ℃.
2. according to the described resin combination of claim 1, wherein monomer comprises the methyl methacrylate monomer of at least 50 weight %.
3. according to the described resin combination of claim 1, wherein methacrylic resin comprises 50 weight % or more methyl methacrylate units.
4. according to the described resin combination of claim 1, wherein elastic granule is the elastic granule with multilayered structure.
5. according to the described resin combination of claim 1, wherein the difference between 10 hours half life temperatures of 10 of the first simple function organo-peroxide hours half life temperatures and the second simple function organo-peroxide is more than or equal to 10 ℃; Difference between 10 hours half life temperatures of the second simple function organo-peroxide and the 10 hours half life temperatures of the 3rd simple function organo-peroxide is more than or equal to 10 ℃.
6. according to the described resin combination of claim 1, wherein the weight ratio of methacrylic resin and elastic granule is 3/7～7/3 in the resin combination; And the gross weight umber by monomer, methacrylic resin and elastic granule is 100 parts, comprises the elastic granule of 10 weight parts～40 weight parts.
7. according to claim 1 or 6 described resin combinations, wherein the weight ratio of the first simple function organo-peroxide and the second simple function organo-peroxide is 3/7～7/3; The weight ratio of the total amount of the first and second simple function organo-peroxides and the 3rd simple function organo-peroxide is 3/7～7/3; And by the monomer weight umber that contains methyl methacrylate monomer is 100 parts, and the gross weight umber scope of first, second and the 3rd simple function organo-peroxide is 0.05～0.5 weight part.
8. a method of making the methacrylic resin moulded parts comprises the step of polymerization according to each described resin combination among the claim 1-7.
9. according to the method for the described manufacturing methacrylic resin of claim 8 moulded parts, wherein polymerization adopts the casting polymerization to carry out.
10. according to the method for the described manufacturing methacrylic resin of claim 9 moulded parts, wherein polymerization employing casting is aggregated in the polymeric pool and carries out.
11. according to the method for the described manufacturing methacrylic resin of claim 8 moulded parts, wherein polymerization is by at 10 hours half life temperature (T than the first simple function organo-peroxide
1) insulation 10 hours or longer under low at least 5 ℃ the temperature, elevated temperature is to 10 hours half life temperature (T than the 3rd simple function organo-peroxide then
3) high at least 5 ℃ temperature and carry out.
12. according to the method for the described manufacturing methacrylic resin of claim 11 moulded parts, wherein polymerization is by at 10 hours half life temperature (T than the first simple function organo-peroxide
1) insulation 10 hours or longer under low at least 5 ℃ the temperature, then at 10 hours half life temperature (T than the first simple function organo-peroxide
1) low about 5 ℃～high about 10 ℃ scope is interior to be incubated 1 hour or longer, again at 10 hours half life temperature (T than the second simple function organo-peroxide
2) low about 10 ℃～high about 10 ℃ scope is interior to be incubated 1 hour or longer, and last elevated temperature is to 10 hours half life temperature (T than the 3rd simple function organo-peroxide
3) high at least 5 ℃ temperature and carry out.
13. methacrylic resin moulded parts that polymerization obtains according to each described resin combination among the claim 1-7.
14. methacrylic resin moulded parts that the casting polymerization obtains according to each described resin combination among the claim 1-7.
15. methacrylic resin moulded parts that polymerization obtains according to each described resin combination among the claim 1-7 in polymeric pool.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP227032/2002 | 2002-08-05 | ||
| JP2002227032A JP2004067789A (en) | 2002-08-05 | 2002-08-05 | Method for manufacturing cast molded article of impact-resistant methacrylate resin |
| JP227032/02 | 2002-08-05 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1488670A true CN1488670A (en) | 2004-04-14 |
| CN1326937C CN1326937C (en) | 2007-07-18 |
Family
ID=32014175
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB03158036XA Expired - Fee Related CN1326937C (en) | 2002-08-05 | 2003-08-04 | Methacrylic acid resin moulded product and its production method and resin compositon for producing said product |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP2004067789A (en) |
| KR (1) | KR20040014252A (en) |
| CN (1) | CN1326937C (en) |
| TW (1) | TWI285661B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103183783A (en) * | 2011-12-28 | 2013-07-03 | 上海贝诺装饰新材料有限公司 | Modified methacrylic resin for making transparent platform basin and preparation method thereof |
| CN109810442A (en) * | 2019-01-24 | 2019-05-28 | 广州秀珀化工涂料有限公司 | MMA- vinyl guide brick and preparation method thereof |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5436989B2 (en) * | 2009-09-08 | 2014-03-05 | 旭化成ケミカルズ株式会社 | Methacrylic resin molded body and method for producing the same |
| KR20140086729A (en) | 2012-12-28 | 2014-07-08 | 제일모직주식회사 | Pransparent thermoplastic resin composition and molded article using the same |
| JP6739988B2 (en) * | 2015-04-30 | 2020-08-12 | 積水化学工業株式会社 | Base particle, method for producing base particle, conductive particle, conductive material, and connection structure |
| FR3053348B1 (en) * | 2016-06-29 | 2020-03-27 | Arkema France | COMPOSITION COMPRISING A MULTI-PHASE POLYMER AND TWO DIFFERENT (METH) ACRYLIC POLYMERS, METHOD FOR PREPARING THE SAME AND ARTICLE THEREOF |
| FR3082845B1 (en) * | 2018-06-21 | 2021-01-15 | Arkema France | LIQUID COMPOSITION COMPRISING THREE INITIATORS, ITS POLYMERIZATION PROCESS, ITS USE AND MATERIAL OBTAINED AFTER POLYMERIZATION OF THE COMPOSITION |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2873107B2 (en) * | 1991-03-29 | 1999-03-24 | 三菱レイヨン株式会社 | Method for producing rubber-containing graft copolymer particles |
| DE4240744A1 (en) * | 1992-12-03 | 1994-06-09 | Wacker Chemie Gmbh | Process for the preparation of a graft copolymer latex of core-shell dispersion particles with improved phase connection between core and shell |
| JPH0816177B2 (en) * | 1993-09-13 | 1996-02-21 | 工業技術院長 | Polymer-metal cluster composite having high elastic modulus and method for producing the same |
| CN1073577C (en) * | 1998-09-30 | 2001-10-24 | 复旦大学 | Process for preparing acrylonitrile, phenylethylene and polyacrylate graft copolymer |
-
2002
- 2002-08-05 JP JP2002227032A patent/JP2004067789A/en active Pending
-
2003
- 2003-08-04 TW TW092121291A patent/TWI285661B/en not_active IP Right Cessation
- 2003-08-04 CN CNB03158036XA patent/CN1326937C/en not_active Expired - Fee Related
- 2003-08-04 KR KR1020030053711A patent/KR20040014252A/en not_active Application Discontinuation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103183783A (en) * | 2011-12-28 | 2013-07-03 | 上海贝诺装饰新材料有限公司 | Modified methacrylic resin for making transparent platform basin and preparation method thereof |
| CN109810442A (en) * | 2019-01-24 | 2019-05-28 | 广州秀珀化工涂料有限公司 | MMA- vinyl guide brick and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1326937C (en) | 2007-07-18 |
| TWI285661B (en) | 2007-08-21 |
| KR20040014252A (en) | 2004-02-14 |
| TW200406459A (en) | 2004-05-01 |
| JP2004067789A (en) | 2004-03-04 |
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