CN1163898A - Process for preparing beads of polymers having acrylic basis - Google Patents
Process for preparing beads of polymers having acrylic basis Download PDFInfo
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- CN1163898A CN1163898A CN 97103181 CN97103181A CN1163898A CN 1163898 A CN1163898 A CN 1163898A CN 97103181 CN97103181 CN 97103181 CN 97103181 A CN97103181 A CN 97103181A CN 1163898 A CN1163898 A CN 1163898A
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Abstract
Process for preparing beads based on acrylic polymers which comprises the preparation of microbeads from 10 to 40 micron by means of a polymerization process in suspension of acrylic monomers in the presence of at least a crosslinking monomer at least bifunctional, characterized in that a second polymerization of the acrylic monomers is carried out in absence of crosslinking monomers and using as suspending phase a fraction of the suspension obtained in the preceding polymerization containing a crosslinking agent, said fraction containing an amount of microbeads comprised between 3 and 40% by weight with respect to the final polymer obtained in the second polymerization.
Description
The present invention relates to prepare and have based on the method for crosslinked polymerizing acrylic acid thing microballon pellet and the microballon grain that makes like this.
Particularly the present invention relates to the crosslinked microballon grain of acrylate copolymer, it is fit to prepare anti-reflecting surface by extrusion method.
The known usefulness of prior art has the 10-40 micron, general about 20 micron-scales, and crosslinked acrylate copolymer microballon grain prepares said anti-reflecting surface.
The commercial run for preparing said microballon grain for example preferably carries out as suspension agent with polyvinyl alcohol in suspension.
The shortcoming of these methods is that the particle of these sizes is difficult to centrifugation.Owing to the viscosity of the water that contains this microballon grain is very high, therefore also need really recently to operate with 3: 1 dilution.
For based on the common bead material of acrylate copolymer (PMMA of mean diameter 200-300 micron for example, the ALTUGLAS of for example commercial ATOHAAS that knows
(R)) centrifugation need operate with 1/5 centrifugation rate.
Relevant from the said microballon grain of further shortcoming of the viewpoint of industry and centrifugation after drying.
In view of the small size of this microballon grain, therefore it need operate in inert atmosphere near limits of explosion.
Yet by the getable productive rate of these methods is 70%.Occur ecological problem thus, the COD of this waste water (chemical oxygen demand (COD)) is 50000ppm.
Therefore need to arrange a commercial run, especially can improve productive rate and reduce COD so that can overcome above said shortcoming.
Really it is noted that to have only uses the microballon grain of above illustrated dimension just can obtain anti-reflecting surface.
Also be to show, if use the very little particle of big 10 multiple lengths just can not obtain anti-reflecting surface by the test that the applicant carries out.
Unexpected now and be surprised to find, if utilize following said preparation method, can produce bead material based on acrylate copolymer, utilize its extrudate can obtain anti-reflecting surface.
Therefore an object of the present invention is to provide the method for a kind of preparation based on the microballon grain of acrylate copolymer, being included at least, there is the microballon grain for preparing the 10-40 micron down by the suspension polymerization of Acrylic Acid Monomer at least a cross-linking monomer of difunctionality base, it is characterized in that second of this Acrylic Acid Monomer is aggregated in the part of the resulting suspension of polymerization that does not have cross-linking monomer and priority of use to contain linking agent as carrying out under the condition of suspending phase, said part contains the 3-40% with respect to the resulting final polymkeric substance of second polymerization, the microballon grain of preferred 4.5-25 weight.
Find that unexpectedly operation can obtain having at least 80 micron-scales under above said condition, the bead material of generally about 150-200 micron utilizes its crowded thing can obtain anti-reflecting surface.
This result is very wondrous, because the general crosslinked bead material with 150-200 micron as mentioned above can not obtain anti-reflecting surface.
A further object of the present invention is included in and replaces water as disperse phase in second polymerization that does not have linking agent, can use the recycle-water from Acrylic Acid Monomer suspension polymerization, and this water generates is greater than the bead material of 100 micron-scales.
In this method, can help industrial polymerization plant to reduce the whole COD that produced, because as known, mother liquor generally is sent to treatment plant to reduce the COD of outlet.
Bead material size according to the present invention is greater than the size of those microballon pellets, generally is the 80-300 micron, preferred 140-250 micron, more preferably 150-200 micron.
Having based on acrylic acid Acrylic Acid Monomer according to polymkeric substance of the present invention as being used to prepare, is linearity or branching (methyl) vinylformic acid C when possibility
1-C
8Alkyl ester, what can mention is, for example: a1) when may the time be one or more acrylic or methacrylic acid C of linearity or branching
1-C
8Alkyl ester, (methyl) methyl acrylate for example, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, (methyl) vinylformic acid be in ester, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate; B1) can select 60% weight at the most, one or more of preferred 50% be soluble monomer in water, its solubleness in water is per 100 gram water at least 5 gram, for example vinylformic acid, methacrylic acid, acrylamide, (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylates under 23 ℃ temperature; C1) can select the another kind of monomer of general maximum 50% weight, for example vinylbenzene, alpha-methyl styrene, (methyl) vinyl cyanide, have 1-10 carbon atom alkyl and 6-12 carbon atom aryl just-alkyl or aryl maleimide, divinyl, styrene sulfonic acid, N-vinyl pyrrolidone.
Superoxide can be used as radical initiator, for example t-butyl peroxy-2-ethylhexanoate, dibenzoyl peroxide, lauroyl peroxide, t-butyl peroxy-2-diethylacetic acid ester or unstable azo-compound for example, Diisopropyl azodicarboxylate.
Can use the C of band linearity or branching as chain-transfer agent
3-C
20, preferred C
1-C
12The alkyl sulfhydryl of alkyl, for example, n-butyl mercaptan, octyl mercaptan, n-dodecane mercaptan, uncle-dodecyl mercaptans, hexanaphthene mercaptan, pianthiol.
When using aforesaid mother liquor, can use according to pointed resulting those materials of polymerization process of clear 457356 (being hereby incorporated by reference) in European patent Shen as disperse phase.
The method that obtains above 10-40 micron microballon grain is that known and this method of prior art is used the suspension agent that can obtain said size microballon grain.
Generally can use spissated polyvinyl alcohol as suspension agent, generally at least 1.5% weight is up to about 10% weight.
Water and monomeric ratio generally are higher than 2: 1, for example 3: 1 in the polymerization of preparation microballon grain.
The linking agent that is used for polymerization first phase be know and as what said is dual functional at least, they generally also are trifunctionals or polyfunctional.They can not be this but acrylic-type, yet must be absolutely necessary.
What for example can mention is allyl methacrylate, Vinylstyrene, dimethacrylate glycidyl esters, Ethylene glycol dimethacrylate (EGDM), dimethacrylate TEG ester (TEGDM).
In second polymerization that does not have linking agent, disperse phase and monomeric ratio can be those shown in first polymerization, also can be low slightly, and for example 1.4: 1.
The characteristic of bead material and microballon grain is undertaken by optical means or definite grain size analysis of sieving; The COD of waste water determines according to IRSA method " chemical oxygen demand (COD) "; Measure the exsiccant residue at 160 ℃ after the centrifugation bead material.
The report in table 2 and 1 respectively of maximally related characteristic and process data.
Provide following example and be used for illustration purpose rather than restriction the present invention.The preparation of the microballon grain that example 1 (Comparative Examples) is crosslinked
In with the suspension agent of methyl methacrylate, ethyl propenoate and allyl methacrylate(AMA), carry out polymerization as suspension agent by use polyvinyl alcohol (PVA).
Deionized water under the 245 weight part room temperatures and 5 weight account polyethylenes alcohol is introduced in that stir, that have jacket layer and the withstand voltage reactor.Under maintenance reactor condition of stirring, it slowly is heated to up to 40 ℃, and temperature is remained on 40 ℃ till polyvinyl alcohol dissolves fully.Remove oxygen by nitrogen gas stream.Add the also mixture of deoxygenation then, it comprises: methyl methacrylate 94.75 weight parts, ethyl propenoate 4 weight parts, allyl methacrylate 0.25 weight part, lauroyl peroxide 0.6 weight part.This reactor seals, and pressure is 100KPa, and this mixture was heated to gradually in 120 minutes and is up to 110 ℃ under continuously stirring.Obtain mean diameter and be 20 microns crosslinked microballon grain (in table, being called XD).The characteristic of this bead material and mother liquor record in table 2.Example 2 preparations contain the female sharp of 7% crosslinked microballon grain
In the same reactor that example 1 has been used, the general operation mode that employing has been stated in said example, the suspension polymerization of methyl methacrylate and ethyl propenoate use a part to carry out as suspension from example 1 said polymeric slurry (microballon grain+water).In this reactor, introduce 188.4 parts by weight of deionized water and 26.9 weight parts slurry then from example 1.This solution is heated to 80 ℃ to add then and comprises methyl methacrylate 96 weight parts, ethyl propenoate 4 weight parts, lauroyl peroxide 0.6 weight part, the mixture of n-butyl mercaptan 0.12 weight part.This reactor seals, and pressure is 100KPa, and this mixture was heated to gradually in 120 minutes and is up to 110 ℃ under continuously stirring.This reactor was kept 15 minutes, cooling then at 110 ℃.Isolate the polymkeric substance of bead material form by centrifugation from mother liquor, with deionized water with its washing and dry in 80 ℃ of bakers.The characteristic of this bead material and mother liquor record in table 2.Example 3-7 preparation contains the masterbatch of various quantity microballon grains
Use in the general operation mode described in the said example in the same reactor that example 2 has been used, said aaerosol solution carries out in the suspension polymerization use table 1 of methyl methacrylate and ethyl propenoate.In this reactor, put into the deionized water and the slurry of the represented amount of table 1 for this reason.
This solution is heated to 80 ℃, adds then and comprise methyl methacrylate 96 weight parts, ethyl propenoate 4 weight parts, lauroyl peroxide 0.6 weight part, the mixture of n-butyl mercaptan 0.12 weight part.This reactor seals, and pressure is 100KPa, and this mixture was heated to gradually in 120 minutes and is up to 110 ℃ under continuously stirring.
This reactor was kept 15 minutes, cooling then at 110 ℃.Isolate the polymkeric substance of bead material form by centrifugation from mother liquor, dry in 80 ℃ of bakers.The characteristic of this bead material and mother liquor record in table 2.The preparation of example 8 suspension agents
In reactor, introduce the NaOH solution and 630 parts by weight of deionized water of 120 weight parts, 40% weight.
Slowly add the 2-acrylamide-2-methyl propane sulfonic acid (AMPS) of 250 weight parts, use a small amount of soda or AMPS additive then the scope of its pH regulator to 7-8.This solution is removed oxygen with nitrogen wash and be heated to after 50 ℃, add 0.075 weight part Potassium Persulphate and 0.025 weight part pyrosulphite hydrogen sodium.Finish after being aggregated in about 60 minutes.Obtain a solution with about 4000 parts by weight of deionized water dilution then, it has the dried residue (at 160 ℃) of 5.5% weight and the brookfield viscosity (25 ℃ of measurements) of 4Pa.s.The preparation of example 9 mother liquors
The sodium salt homopolymer of resulting 2-acrylamide-2-methyl propane sulfonic acid in the use-case 8 is carried out as suspension agent.
What stir, introduce resulting solution in 193 parts by weight of deionized water and the 7 weight part examples 8 in strap clamp cover and the voltage-resistant reactor, be equivalent to 0.385 weight part in dry product.Remove oxygen and this solution is heated to 80 ℃ with nitrogen gas stream.Add 100 weight parts (it also is deoxidation) mixture then, it comprises: methyl methacrylate 96 weight parts, ethyl propenoate 4 weight parts, t-butyl peroxy-2-ethylhexanoate 0.25 weight part, n-butyl mercaptan 0.12 weight part.This reactor seals, and pressure is 100KPa, and this mixture was heated to gradually in 120 minutes and is up to 110 ℃ under continuously stirring.This reactor was kept 15 minutes, cooling then at 110 ℃.Isolate the polymkeric substance of bead material form by centrifugation from mother liquor, dry in 80 ℃ of bakers then with deionized water wash.Bead material is of a size of 200 microns.
To have about 0.62% mother liquor that overweights dry resistates (160 ℃) (it partly comprises suspension agent (0.2% weight) and remainder is the other products of gained in the polymerization) combines and is used for afterwards aggregation test.Example 10 preparations contain the masterbatch of 7% crosslinked microballon grain
In the same reactor that example 2 has been used, use in the general operation mode described in the said example, the suspension polymerization of methyl methacrylate and ethyl propenoate uses a part to carry out as suspension from example 1 said polymeric slurry (microballon grain+water) with from the mother liquor of example 9.So in this reactor, introduce 188.4 weight parts from the water-bearing mother liquor of example 9 and 27.2 weight parts slurry from example 1.This solution is heated to 80 ℃ to add then and comprises methyl methacrylate 96 weight parts, ethyl propenoate 4 weight parts, lauroyl peroxide 0.6 weight part, the mixture of n-butyl mercaptan 0.12 weight part.This reactor seals, and pressure is 100KPa, and this mixture was heated to gradually in 120 minutes and is up to 110 ℃ under continuously stirring.This reactor was kept 15 minutes, cooling then at 110 ℃.Isolate the polymkeric substance of bead material form by centrifugation from mother liquor, with deionized water wash then in 80 ℃ of bakers in dry.The characteristic of this bead material and mother liquor record in table 2.The bead material that example 11 (comparative example) preparation is crosslinked
In the same reactor that example 2 has been used, use is in the general operation mode described in the said example, the suspension polymerization of methyl methacrylate, ethyl propenoate and allyl methacrylate(AMA) uses a part of mother liquor from example 9 to carry out polymerization as suspension.
So in this reactor, introduce the water-bearing mother liquor of 200 weight parts from example 9.This solution is heated to 80 ℃ to add then and comprises methyl methacrylate 94.75 weight parts, ethyl propenoate 4 weight parts, allyl methacrylate(AMA) 0.25 weight part, the mixture of lauroyl peroxide 0.6 weight part.
This reactor seals, and pressure is 100KPa, and this mixture was heated to gradually in 120 minutes and is up to 110 ℃ under continuously stirring.
This reactor was kept 15 minutes, cooling then at 110 ℃.Isolate the polymkeric substance of bead material form by centrifugation from mother liquor, with deionized water wash then in 80 ℃ of bakers in dry.
This bead material has 200 microns size.Extruding of example 12 anti-reflection plates
The bead material of preparation begins from example 1,2,9 and 11, and extruding 5cm * 10cm thickness with the composition that is write down in the table 3 is the plate of 2-3mm so that test its antireflective property.All plates all contain the cross-linked particles of 6% weight.The evaluation of sheet material outward appearance is with the naked eye carried out.
In fact this test is performed as follows: will be placed on the surface of containing print character by the sheet material of extruding preparation.
The sheet material (plate 1 and 2) that begins to extrude from the microballon grain from example 1 and 2 has good antireflective property, promptly they can make you see definitely be placed on following table and print character just look like like they do not exist.
Plate 3 from the bead material of the bead material of example 9 and example 11 begins to extrude does not show antireflective property antithesis, that is, the character of lower surface manifests distortion.Therefore plate 3 does not have qualified antireflective property.
Table 1
The composition of water (per 100 parts of monomers)
| Embodiment | XD in the masterbatch | Deionized water | Slurry (from example 1) | Water/monomer ratio | Polyvinyl alcohol |
| % weight | Weight part | Weight part | W/w | % at aqueous phase | |
| ????1 | ????- | ????250.0 | ????- | ????2.500 | ????2.00 |
| ????2 | ????7 | ????188.6 | ????26.9 | ????1.929 | ????0.25 |
| ????3 | ????14 | ????175.2 | ????58.3 | ????1.859 | ????0.50 |
| ????4 | ????14 | ????175.2 | ????58.3 | ????1.859 | ????0.50 |
| ????5 | ????20 | ????161.8 | ????89.8 | ????1.798 | ????0.71 |
| ????6 | ????20 | ????161.8 | ????89.8 | ????1.798 | ????0.71 |
| ????7 | ????30 | ????134.3 | ????154.6 | ????1.697 | ????0.93 |
Table 2
Characteristic
(1) based on masterbatch (6% means the quantity of XD suspensoid, and it contains 60 weight part bead materials and diluted emulsion and is used for monomer at the second reaction polymerization, 940 weight parts); (2) waste material; (3) COD of mother liquor; (4) XD standard method
| Embodiment | XD in the masterbatch | Dried residue at 160 ℃ | Screening＞1mm | ??COD | Productive rate | The bead material mean diameter |
| ????(1) | ????(2) | ????(3) | ||||
| % weight | % weight | % weight | ??ppm | % weight | ??μmm | |
| ????1(4) | ????- | ????6.50 | ??57000 | ??70 | ????20 | |
| ????2 | ????7 | ????1.14 | ????10.1 | ??8010 | ??98.8 | ????210 |
| ????3 | ????14 | ????0.97 | ????2.1 | ??7807 | ??99.1 | ????180 |
| ????4 | ????14 | ????1.46 | ????0.3 | ??11610 | ??98.5 | |
| ????5 | ????20 | ????1.06 | ????0.0 | ??10960 | ??99.4 | ????160 |
| ????6 | ????20 | ????1.16 | ????0.0 | ??10480 | ??99.4 | |
| ????7 | ????30 | ????1.89 | ????0.0 | ??19390 | ??98.9 | ????150 |
| ????10 | ????7 | ????1.30 | ????8.1 | ??9300 | ??98.1 | ????190 |
Table 3
The preparation of anti-reflection plate
| Plate | Bead material example 9 | Routine number of bead material | |
| Weight part | Weight part | ||
| ????1 | ????94.0 | ????1 | ????6.0 |
| ????2 | ????14.3 | ????2 | ????85.7 |
| ????3 | ????94.0 | ????11 | ????6.0 |
Claims (9)
1 preparation is based on the method for acrylate copolymer bead material, being included at least, there is the microballon grain for preparing the 10-40 micron down by the suspension polymerization of Acrylic Acid Monomer at least a cross-linking monomer of difunctionality base, it is characterized in that a part that second of this Acrylic Acid Monomer is aggregated in the resulting suspension of polymerization that does not have cross-linking monomer and priority of use to contain linking agent as carrying out under the condition of suspending phase, said part contains the microballon grain with respect to the 3-40% weight of the resulting final polymkeric substance of second polymerization.
2 according to the process of claim 1 wherein that the resulting a part of suspension of the polymerization that formerly contains linking agent is used as suspension agent, and said part contains the microballon grain of 4.5-25 quantity.
3 methods according to claim 1-2 wherein replace water as disperse phase with waste water in second polymerization that does not have linking agent, can select dilute with water, and it is from the suspension polymerization of Acrylic Acid Monomer, and this water generates is greater than the bead material of 100 micron-scales.
4 methods according to claim 1-3, the Acrylic Acid Monomer that wherein is used to prepare the polymkeric substance with acrylic is linearity or branching (methyl) vinylformic acid C when possibility
1-C
8Alkyl ester is selected from a1) (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) isopropyl acrylate, butyl acrylate, (methyl) sec-butyl acrylate, (Dan Ji) tert-butyl acrylate; B1) can select 50% one or more soluble monomer in water of measuring, its solubleness in water is per 100 gram water at least 5 grams under 23 ℃ temperature, and this monomer is selected from vinylformic acid, methacrylic acid, acrylamide, (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate; C1) can select the another kind of monomer of maximum 50% weight, it is selected from vinylbenzene, alpha-methyl styrene, (methyl) vinyl cyanide, have 1-10 carbon atom alkyl and 6-12 carbon atom aryl just-alkyl or aryl maleimide, divinyl, styrene sulfonic acid, N-vinyl pyrrolidone.
5 methods according to claim 1-4 are wherein having in first polymerization in the presence of the linking agent polyvinyl alcohol as suspension agent, and its concentration is at least 1.5% weight and be up to about 10% weight generally.
6 methods according to claim 1-5, wherein in the presence of linking agent is arranged in the polymerization of preparation microballon grain water and monomeric ratio be higher than 2: 1.
7 methods according to claim 1-6, wherein water and monomeric ratio are 1.4: 1 or higher in the polymerization that does not have linking agent.
8 by the available bead material based on acrylate copolymer with 80-300 micron-scale of the method for claim 1-7.
9 according to Claim 8 based on the bead material with size between 140 and 250 microns of acrylate copolymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97103181 CN1163898A (en) | 1996-02-19 | 1997-02-19 | Process for preparing beads of polymers having acrylic basis |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| ITMI96A000312 | 1996-02-19 | ||
| CN 97103181 CN1163898A (en) | 1996-02-19 | 1997-02-19 | Process for preparing beads of polymers having acrylic basis |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1163898A true CN1163898A (en) | 1997-11-05 |
Family
ID=5166561
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 97103181 Pending CN1163898A (en) | 1996-02-19 | 1997-02-19 | Process for preparing beads of polymers having acrylic basis |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1163898A (en) |
-
1997
- 1997-02-19 CN CN 97103181 patent/CN1163898A/en active Pending
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