CN101445577A - Preparation method for functional polyolefin with blocked isocyanate functional group - Google Patents
Preparation method for functional polyolefin with blocked isocyanate functional group Download PDFInfo
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- CN101445577A CN101445577A CNA2008100514264A CN200810051426A CN101445577A CN 101445577 A CN101445577 A CN 101445577A CN A2008100514264 A CNA2008100514264 A CN A2008100514264A CN 200810051426 A CN200810051426 A CN 200810051426A CN 101445577 A CN101445577 A CN 101445577A
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Abstract
The invention provides a preparation method for functional polyolefin with a blocked isocyanate functional group. Mechanical mixing is carried out on polyolefin resin, a peroxide initiator and a functional monomer with a blocked isocyanate functional group; a reaction squeezing grafting method is used to lead the polyolefin resin to take grafting reaction with the functional monomer in a fusion state, thus obtaining the functional polyolefin with the blocked isocyanate functional group. The functional polyolefin with the blocked isocyanate functional group prepared by the invention not only overcomes the defects of being sensitive to humidity and large toxicity in the grafting process of the fusion reaction of the isocyanate monomers used as the functional monomer, and is different from common functional polyolefin which only has excellent compatibility with one from daiamid and polyester; the prepared functional polyolefin with the blocked isocyanate functional group also has excellent compatibility and responsivity with the daiamid and the polyester.
Description
Technical field
The present invention relates to a kind of preparation method of functional polyolefin resin, a kind of specifically preparation method of the functional polyolefin with masked isocyanate functional group.
Background technology
Polyolefine has good mechanical performance, electrical property and chemical stability, and it is cheap, is used widely in a lot of fields.Yet, because such material is non-polar material, caused its dyeability, wetting ability and with the bad adhesion of metal, inorganic materials, do not have consistency etc. with the polarity polymer, limited the further expansion of its range of application.With unsaturated function monomer of polarity and polyolefin resin copolymerization, the preparation functional polyolefin resin is the universal method that overcomes above shortcoming.Isocyanic ester is the functional group that a class has high reaction activity, can chemical reaction take place with functional groups such as hydroxyl, amino, carboxyl, acid anhydrides, hydramine, phenol, mercaptan, ureas, but because it is not used widely in the preparation functional polyolefin resin to lacking moisture-sensitive, poor stability, storage period.We have proposed the synthetic method that a class contains the masked isocyanate of alpha-olefinic bond in (CN1171862C) in patent of invention " synthetic method that contains the masked isocyanate of alpha-olefinic bond ", have overcome the short shortcoming of poor stability, storage period of band free isocyanate functional group's compound.This compounds at room temperature has very high package stability, and (170～250 ℃) rapid deblocking discharges the free isocyanate groups under higher temperature, with the functional group that contains reactive hydrogen chemical reaction takes place.
Summary of the invention
The invention provides the function monomer of a class band masked isocyanate functional group and the preparation method that the functional polyolefin resin of masked isocyanate functional group is with in the preparation of polyolefin resin reaction extruding graft.
The preparation method's of the functional polyolefin of band masked isocyanate functional group step and condition are as follows:
(A) polyolefin resin 100 weight parts, the function monomer of the band masked isocyanate functional group of adding 0.5-20 weight part, the peroxide initiator of 0.05-5 weight parts mixed 5-10 minute, obtained pre-mixed resin;
(B) pre-mixed resin of (A) gained is joined carry out the fusant reaction extruding graft in the reactor, temperature of reaction is 130-240 ℃, reaction times is 1-10 minute, by the frit reaction grafting masked isocyanate is grafted on the polyolefine macromole, obtains functional polyolefin resin with masked isocyanate functional group.
Polyolefine is a kind of in polyethylene, polypropylene, ethylene propylene rubber, terpolymer EP rubber, polystyrene-poly divinyl-polystyrene block copolymer, polystyrene-poly isoprene-polystyrene block copolymer, polystyrene-hydrogenation (polyhutadiene)-polystyrene block copolymer, the ethylene-octene copolymer in described (A);
The function monomer of band masked isocyanate functional group is that structural formula is a kind of in (I)-(IV) in described (A):
(I) caprolactam blocking (3-isocyanate group-4-methyl) carbaniloyl-2-propylene ester (CLBTAI)
(II) caprolactam blocking isocyanate methylene-3,5,5-trimethylammonium carboxylamine (methacrylic acid acyl-oxygen-2-ethyl) ester (CLBPMAI)
(III) cyclohexanone-oxime end-blocking (3-isocyanate group-4-methyl) carbaniloyl-2-propylene ester (CTBTAI)
(IV) cyclohexanone-oxime blocked isocyanate methylene-3,5,5-trimethylammonium carboxylamine (methacrylic acid acyl-oxygen-2-ethyl) ester (CTBPMAI)
Peroxide initiator is 2,5 dimethyl-2 in described (A), a kind of in 5-bis(t-butylperoxy) hexane (DBPH), dicumyl peroxide (DCP), the benzoyl peroxide (BPO);
Reactor is Banbury mixer, single screw extrusion machine or twin screw extruder in described (B); When adopting Banbury mixer as reactor, temperature of reaction is the 140-230 degree, and rotor speed is 30-100rpm, and the reaction times is 4-10 minute; When adopting single screw rod as reactor, temperature of reaction is the 130-230 degree, and single screw speed is 20-70rpm, and the reaction times is 1-3 minute; When adopting twin screw as reactor, temperature of reaction is set at the 130-240 degree, and feed screw and driving screw rotating speed are set at 30-400rpm, 40-150rpm respectively.The structural characterization and the performance test of the functional polyolefin of the band masked isocyanate functional group that the present invention relates to are as follows:
Dissolving-settling step commonly used is adopted in the purification of sample: promptly elder generation in the xylene solvent of heat, is precipitated sample dissolution then with acetone solvent, filters, and washing obtains purified product after the drying.
The calculation formula that not dissociated isocyanic ester accounts for the per-cent that is grafted to the masked isocyanate on the polymkeric substance in the graft copolymer is as follows:
(A wherein
NCO/ A
CO)
g, (A
NCO/ A
CO)
0Be respectively the purification grafts, the height ratio of the absorption peak of isocyanate groups NCO and the carbonyl CO that closes on alpha-olefinic bond, generate by hydroxyl and isocyanate groups reaction in the monomer during not with end-capping reagent;
Monomeric percentage of grafting obtains according to the elemental analysis method of purification grafts.
The bonding T type stripping strength reference standard GB/T 2791-1995 of functional polyolefin and other material, bonding sample is the fusion compression molding, peeling rate 50mm/min; Stripping strength comprises the stripping strength δ of grafts and metallic aluminium
t(Al), the stripping strength δ of grafts and nylon 6
t(PA6), the stripping strength δ of grafts and polybutylene terephthalate
t(PBT).The sample of all stripping tests all is to carry out compression molding more than 200 degree, guarantee isocyanate groups release and with the reaction of active group.
Advantage of the present invention is: the toxicity in (1) reaction extruding graft process is lower; (2) monomer autohemagglutination tendency in the grafting process is lower; (3) monomer that is grafted on the molecular polyolefin main chain can partly discharge isocyanic ester, has both guaranteed that monomer can dissociate, and had guaranteed monomeric closure again; (3) isocyanate groups that masked isocyanate discharged that is grafted on the polymer molecule main chain has very high reactive behavior; (4) polyolefine material of masked isocyanate functionalization not only has good cementability with metal (aluminium), polymeric amide PA, polyester, therefore can be used as toughner is used for polyolefin/polyamide, the preparation of polyolefine/polyester alloy material or be used for polyolefin/polyamide/inorganic particulate, the compatibilization and toughening of polyolefine/polyester/inorganic particulate.The polyolefine of the masked isocyanate functionalization of the present invention preparation not only overcome the isocyanates monomer as function monomer in frit reaction grafting process to moisture-sensitive, shortcoming that toxicity is big, and be different from general functional polyolefin often only with polymeric amide, polyester in a kind ofly have a good consistency, masked isocyanate functional polyolefin and polymeric amide, the polyester of preparation have good consistency, reactivity simultaneously.
Description of drawings
Fig. 1 is the infrared spectrum of ethylene-octene copolymer and grafting caprolactam blocking (3-isocyanate group-4-methyl) carbaniloyl-2-propylene ester thereof.We can see, with respect to the ethylene-octene copolymer of functionalization not, in the infrared spectrum of the ethylene-octene copolymer grafting caprolactam blocking after the functionalization (3-isocyanate group-4-methyl) carbaniloyl-2-propylene ester at 2272cm
-1And 1720cm
-1The charateristic avsorption band of isocyanate groups and carbonyl has appearred respectively in the place, illustrates that caprolactam blocking (3-isocyanate group-4-methyl) carbaniloyl-2-propylene ester successfully is grafted on the ethylene-octene copolymer molecule.
Embodiment
Below in conjunction with example, the present invention is set forth, but the invention is not restricted to following specific examples.The umber of the various raw materials among the embodiment is mass fraction.
Embodiment 1
Choose 100 parts ethylene-octene copolymer POE, 3 parts masked isocyanate function monomer I, 0.2 part of benzoyl peroxide BPO mixes in homogenizer after 3 minutes under the room temperature, adds in the Banbury mixer and carries out reactive grafting.Wherein the melt flow rate (MFR) of POE is 5g/10min, and form is granular, and BPO is commercially available analytical reagent, and the cavity volume of Banbury mixer is 50ml, and the frit reaction processing temperature is set at 145 ℃, and rotor speed is 60rpm.The characterization test of products therefrom as shown in Table 1, the infrared figure of POE and grafts thereof (POE-g-BTAI) sees shown in the figure one.
Comparative example 1
Function monomer among the embodiment 1 is changed into maleic anhydride MAH, and all the other conditions are identical, and the adhesiveproperties of gained result product sees Table shown in one.
Embodiment 2
With 100 parts of polystyrene-(polyhutadiene)-polystyrene triblock copolymer elastomerics (4.5g/10min, 190 ℃, 2.16kg), 3 parts of masked isocyanate function monomer II, 0.1 part 2,5-dimethyl-2,5-bis(t-butylperoxy) hexane DBPH stirs the machine mixing after 3 minutes at height, joins and carries out reactive grafting in the twin screw extruder.Wherein elastomeric MFR be 2.5g/10min (190 ℃, 2.16kg), polystyrene, polybutadiene content ratio are 24/76 (wt/wt), form is a granular solids; DCP is commercially available analytical reagent; The diameter of twin screw is 30mm, length-to-diameter ratio is 44, and setting twin screw is 135-180 ℃ along charging opening to a mouthful mould direction temperature, and the temperature of engagement reaction zone is set at 180 ℃, die temperature is set at 175 ℃, and feed screw and twin screw rotating speed are set at 150rpm and 50rpm respectively.The characterization test of gained grafts as shown in Table 1.
Comparative example 2
Function monomer among the embodiment 2 is changed into glycidyl methacrylate GMA, and all the other conditions are identical, and the adhesiveproperties of gained result product sees Table shown in one.
Embodiment 3
Choose 100 parts of polystyrene-hydrogenations (polyhutadiene)-polystyrene triblock copolymer elastomerics (230 ℃ of MFR=1.83g/10min, 2.16kg, form is a powder), 5 parts of masked isocyanate function monomer I, 0.3 part 2,5-dimethyl-2 joins after the 5-bis(t-butylperoxy) hexane DBPH pre-mixing and carries out the frit reaction grafting in the twin screw extruder.The diameter of twin screw is 30mm, and setting twin screw is 135-230 ℃ along charging opening to a mouthful mould direction temperature, and the temperature of engagement reaction zone is set at 230 ℃, and die temperature is set at 210 ℃, and feed screw and twin screw rotating speed are set at 300rpm and 50rpm respectively.Product is granulation after extruding, and drying characterizes, and the gained characterization data sees Table one.
Comparative example 3
Function monomer among the embodiment 3 is changed into vinylformic acid AA, and all the other conditions are identical, and the adhesiveproperties of gained result product sees Table shown in one.
Embodiment 4
Choose 100 parts granular terpolymer EP rubber (MFR=10g/10min, 190 ℃, 2.16kg), 4 parts masked isocyanate IV, 0.3 the dicumyl peroxide DCP mechanically mixing of part joins Banbury mixer later on and carries out reactive grafting, wherein DCP is commercially available analytical reagent, the cavity volume of Banbury mixer is 50ml, and the frit reaction processing temperature is set at 175 ℃, and rotor speed is 60rpm.The characterization test of gained grafts as shown in Table 1.
Comparative example 4
Function monomer among the embodiment 4 is changed into hydroxyethyl methylacrylate HEMA, and all the other conditions are identical, and the adhesiveproperties of gained result product sees Table shown in one.
Embodiment 5
With 100 parts of powder linear low density polyethylenes (MFR=2.1g/10min, 190 ℃, 2.16kg), 2.5 part masked isocyanate III, 0.15 part of dicumyl peroxide (DCP, analytical pure) mixes after 3 minutes in homogenizer, joining twin screw extruder reacts and extrudes granulation.Wherein the twin screw diameter is 24mm, length-to-diameter ratio is 40, and setting twin screw is 135-200 ℃ along charging opening to a mouthful mould direction temperature, and the temperature of engagement reaction zone is set at 200 ℃, die temperature is set at 180 ℃, and feed screw and twin screw rotating speed are set at 200rpm and 75rpm respectively.The test of products therefrom characterizes as shown in Table 1.
Embodiment 6
Take by weighing 100 parts of Co-polypropylene, 6 parts masked isocyanate function monomer II, 0.1 part dimethyl-2,5-bis(t-butylperoxy) hexane DBPH, mechanically mixing joins later on carries out frit reaction in the single screw extrusion machine.Wherein the melt flow rate (MFR) of PP be 3.3g/10min (230 ℃, 2.16kg), ethylene content is 10%, form is a powder; DCP is commercially available analytical reagent, the diameter of single screw rod is 70mm, and setting single screw rod is 135-180 ℃ along charging opening to a mouthful mould direction temperature, and the temperature of main reaction region is set at 180 ℃, die temperature is set at 175 ℃, and feed screw and twin screw rotating speed are set at 200rpm and 150rpm respectively.Product is through granulation, drying.Products therefrom is characterized, and data see Table shown in one.
Embodiment 7
Take by weighing 100 parts of ethylene propylene rubbers, 4 parts masked isocyanate function monomer III, 0.1 part dicumyl peroxide DCP, mechanically mixing joins later on carries out reactive grafting in the Banbury mixer.The cavity volume of Banbury mixer is 50ml, and the frit reaction processing temperature is set at 190 ℃, and rotor speed is 80rpm.The test of products therefrom characterizes as shown in Table 1.
Embodiment 8
Choose polystyrene-poly isoprene-polystyrene block copolymer of 100 parts, 3 parts masked isocyanate function monomer I, 0.1 part dicumyl peroxide DCP.All the other conditions are identical with embodiment 2.The test of products therefrom characterizes as shown in Table 1.
Subordinate list one
| GD (wt％) | X blocked％ | MFR g/10min | δ t(Al) kN/m | δ t(PA6) kN/m | δ t(PBT) kN/m | |
| Embodiment 1 | 1.4 | 87.2％ | 3.7 | 6.8 | Tear | Tear |
| Comparative example 1 | 1.1 | - | 4.7 | 4.5 | 6.2 | 2.3 |
| Embodiment 2 | 1.2 | 64.6 | 4.2 | 4.8 | Tear | Tear |
| Comparative example 2 | 0.8 | - | 5.3 | 2.1 | 3.4 | 5.4 |
| Embodiment 3 | 1.4 | 50.5 | 3.05 | 7.2 | 10.6 | 9.3 |
| Comparative example 3 | 1.7 | - | 3.6 | 5.8 | 4.3 | 5.2 |
| Embodiment 4 | 0.9 | 73.3 | 4.6 | 4.25 | 7.5 | 6.3 |
| Comparative example 4 | 1.05 | - | 5.6 | 2.1 | 2.3 | 3.5 |
| Embodiment 5 | 0.87 | 70.4 | 1.5 | 5.8 | 8.5 | 7.1 |
| Embodiment 6 | 2.03 | 65.8 | 5.5 | 4.8 | 5.6 | 6.8 |
| Embodiment 7 | 1.13 | 70.5 | 2.1 | 6.5 | 8.7 | 6.1 |
| Embodiment 8 | 0.82 | 60.2 | 1.9 | 5.2 | 9.8 | 7.5 |
Claims (5)
1, the preparation method of the functional polyolefin of band masked isocyanate functional group is characterized in that step and condition are as follows:
(A) polyolefin resin adds the function monomer of the band masked isocyanate functional group of 0.5-20 weight part in 100 weight parts, and the peroxide initiator of 0.05-5 weight parts mixed 5-10 minute, obtained pre-mixed resin;
(B) pre-mixed resin of (A) gained is joined carry out the fusant reaction extruding graft in the reactor, temperature of reaction is 130-240 ℃, reaction times is 1-10 minute, by the frit reaction grafting masked isocyanate is grafted on the polyolefine macromole, obtains functional polyolefin resin with masked isocyanate functional group.
2. the preparation method of the functional polyolefin of band masked isocyanate as claimed in claim 1 functional group is characterized in that polyolefine in described (A) is a kind of in polyethylene, polypropylene, ethylene propylene rubber, terpolymer EP rubber, polystyrene-poly divinyl-polystyrene block copolymer, polystyrene-poly isoprene-polystyrene block copolymer, polystyrene-hydrogenation (polyhutadiene)-polystyrene block copolymer, the ethylene-octene copolymer.
3. the preparation method of the functional polyolefin of band masked isocyanate as claimed in claim 1 functional group is characterized in that masked isocyanate function monomer in described (A) is that the function monomer of band masked isocyanate functional group in described (A) is that structural formula is a kind of in (I)-(IV):
(I) caprolactam blocking (3-isocyanate group-4-methyl) carbaniloyl-2-propylene ester
(II) caprolactam blocking isocyanate methylene-3,5,5-trimethylammonium carboxylamine (methacrylic acid acyl-oxygen-2-ethyl) ester
(III) cyclohexanone-oxime end-blocking (3-isocyanate group-4-methyl) carbaniloyl-2-propylene ester
(IV) cyclohexanone-oxime blocked isocyanate methylene-3,5,5-trimethylammonium carboxylamine (methacrylic acid acyl-oxygen-2-ethyl) ester
4. the preparation method of the functional polyolefin of band masked isocyanate as claimed in claim 1 functional group, it is characterized in that peroxide initiator is 2 in described (A), 5 dimethyl-2, a kind of in 5-bis(t-butylperoxy) hexane, dicumyl peroxide, the benzoyl peroxide.
5. the preparation method of the functional polyolefin of band masked isocyanate as claimed in claim 1 functional group is characterized in that reactor is Banbury mixer, single screw extrusion machine or twin screw extruder in described (B); Described Banbury mixer reactor, temperature of reaction are the 140-230 degree, and rotor speed is 30-100rpm, and the reaction times is 4-10 minute; Described single screw reactor, temperature of reaction are the 130-230 degree, and single screw speed is 20-70rpm, and the reaction times is 1-3 minute; Described double-screw reactor, temperature of reaction are set at the 130-240 degree, and feed screw and driving screw rotating speed are set at 30-400rpm, 40-150rpm respectively.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105026479A (en) * | 2013-02-26 | 2015-11-04 | 富士胶片株式会社 | Cellulose acylate film, novel compound, polarizing plate, and liquid crystal display device |
| US10113040B2 (en) | 2014-09-03 | 2018-10-30 | Fujifilm Corporation | Polymer film, polarizing plate and liquid crystal display device |
| CN114479216A (en) * | 2022-03-14 | 2022-05-13 | 河南绿色快车橡塑制品有限公司 | Secondary transfer roller and production process |
-
2008
- 2008-11-17 CN CNA2008100514264A patent/CN101445577A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105026479A (en) * | 2013-02-26 | 2015-11-04 | 富士胶片株式会社 | Cellulose acylate film, novel compound, polarizing plate, and liquid crystal display device |
| JPWO2014133041A1 (en) * | 2013-02-26 | 2017-02-02 | 富士フイルム株式会社 | Cellulose acylate film, novel compound, polarizing plate and liquid crystal display device |
| CN105026479B (en) * | 2013-02-26 | 2017-10-27 | 富士胶片株式会社 | Cellulose acylate film, noval chemical compound, polarizer and liquid crystal display device |
| US10040754B2 (en) | 2013-02-26 | 2018-08-07 | Fujifilm Corporation | Cellulose acylate film, novel compound, polarizing plate and liquid crystal display device |
| US10113040B2 (en) | 2014-09-03 | 2018-10-30 | Fujifilm Corporation | Polymer film, polarizing plate and liquid crystal display device |
| CN114479216A (en) * | 2022-03-14 | 2022-05-13 | 河南绿色快车橡塑制品有限公司 | Secondary transfer roller and production process |
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