CN101434681B - High melt strength acrylic resin and preparation - Google Patents
High melt strength acrylic resin and preparation Download PDFInfo
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- CN101434681B CN101434681B CN2008100516132A CN200810051613A CN101434681B CN 101434681 B CN101434681 B CN 101434681B CN 2008100516132 A CN2008100516132 A CN 2008100516132A CN 200810051613 A CN200810051613 A CN 200810051613A CN 101434681 B CN101434681 B CN 101434681B
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Abstract
The invention relates to a preparation method of high-melt-strength polypropylene. In the method, reactive blending is carried out to polypropylene, monomer with double bonds and dithiocarbamates. The method can significantly improve the melt strength of polypropylene, greatly inhabit the degradation of polypropylene in the reaction process, also greatly decrease the amount of polyfunctional monomer, and save manufacturing cost. The tensile strength can reach 39MPa; the tensile modulus 810MPa; the elongation at break 738 percent; crystallization temperature 113 DEG C to 225 DEG C; the melt index 0.5g/10min to 2.0g/10min; the melt strength 16cN to 36cN; and the gel content 0 percent. No bad effect is brought to the processing performance of the melt and the high-melt-strength polypropylene prepared is applicable to application fields, such as foaming, thermoforming, film blowing and extrusion coating and the like.
Description
Technical field
The present invention relates to a kind of high bath strength acrylic resin and preparation method.
Background technology
Polypropylene is a kind of thermoplasticity synthetic resins of excellent property, have advantages such as little, nontoxic, the easy processing of proportion, resistance to impact shock and electrical insulating property are good, be the best product of thermotolerance in the resins for universal use, have at aspects such as automotive industry, household electrical appliance, electronics, packing and building materials furniture widely and use.But because polypropylene molecular chain be linear structure substantially, softening temperature and fusing point are approaching during heating, melt strength is low, the vertical property of refractory is poor, have limited its application in fields such as thermoforming, extrusion coated, foaming and blowings.Therefore, the raising melt strength of polypropylene is the important topic in the polypropylene new product development always.
Improving melt strength of polypropylene at present mainly realizes by following approach: a class is to improve the way of polypropylene molecule amount and distribution and introducing side chain.Another kind of is that polypropylene is being added man-hour and other amorphous or blend such as low crystalline resins, elastomerics, corresponding raising melting range and melt strength.Specific implementation method mainly contains: x ray irradiation x method, reaction extrusion molding, polymeric kettle method, solution grafting, dynamic crosslinking method, melt blending modification method etc.
With the commodity linear polypropylene is raw material, and the high melt strength, propylene that has the chain of drawing money on credit by the free radical reaction preparation is the main at present research focus of concentrating.
Producing free radical by radiation, introduce the method for branched structure on the line style polypropylene chains, is the industrial method of more successfully preparing high melt strength, propylene at present.Montell company (EP0351866, US6306970) adopts the method for crosslinking electron beam irradiation to prepare long-chain branching polypropylene, and has found a kind of method for preparing long-chain branching polypropylene when being lower than 80 ℃.For effective grafting efficiency that improves, the carrying out of control degradation reaction, Borealis company (DE19693439) has further developed a kind of new method for preparing branched p 0 lypropylene.They add a kind of the 3rd monomer when the irradiation system is carried out free radical reaction, monomeric adding can effectively promote polyacrylic linked reaction when high temperature.The x ray irradiation x method is simple, does not need catalyzer, can react at normal temperatures, and percentage of grafting is controlled easily, existing a large amount of patent report.But this class methods equipment complex and expensive, effectively radiation thickness is restricted.
Be lower than under the melting point polymer temperature, to solid-state or between solid-state and molten state polymkeric substance carry out peroxide treatment, in the superoxide initiation grafting long branched chain structure method, Himont house journal (US5047485, EP0384431) and Chisso house journal (US5416169) have introduced and have selected two kinds of high and low differing temps type peroxide modified solid phase PP under a kind of low temperature for use, the long-chain branching polypropylene method of preparation gel-free.Simultaneously Himont company (CN1045107, CN1055372) patent has been introduced a kind ofly under deoxidation and suitable temp, adds superoxide such as peroxide-butyl carbonate and causes, heating or add as thiomethyl alcohol and make the preparation method of free radical inactivation.Such preparation method is had relatively high expectations to technical qualification, and most proceed step by step, and facility investment is bigger.
Reactive extrusion technology has obtained very fast development in recent years, and has begun to be applied to the production of high melt strength, propylene owing to have efficient, economical and practical advantage.
Patent (CN1432596A) adopts superoxide (2,5-dimethyl-2, two (tert-butyl hydroperoxide) hexanes of 5-) with diacrylate-1, the acetone soln of 6-butanediol ester mixes, in the twin screw extruder stage casing, join in the forcing machine melt polypropylene by volume pump, carry out grafting, obtain high bath strength acrylic resin.Patent (CN1693330A) has been introduced a kind of preparation method of the branched p 0 lypropylene that is suitable for foaming.This method with a small amount of initiator, contain to join after two key simple linear polymers and second monomer (vinylbenzene) and polypropylene mix to react to extrude in the twin screw extruder and prepare polypropylene dedicated material with higher melt intensity.
In above-mentioned report, all adopt superoxide as initiator, the introducing meeting of superoxide produces bigger influence to polyacrylic palliating degradation degree, makes reaction conditions control become complicated.Patent CN200610017181.4 adopts original position thermal initiation grafted method to prepare high bath strength acrylic resin, abandons the traditional technology of using superoxide to cause the preparation high melt strength, propylene.CN200610163256 adopts original position thermal initiation grafted method, and acrylic ester compound and polypropylene fusion graft have been prepared high bath strength acrylic resin.Original position thermal initiation grafting preparation method has effectively controlled polyacrylic degraded, has improved melt strength.But how further to improve monomer-grafted rate and melt strength, also need carry out deep research.
Because the introducing of superoxide can make polypropylene that degraded significantly takes place in the preparation feedback process, greatly reduces polyacrylic mechanical property.In order to suppress polyacrylic excessive degradation, promote the grafting branching reaction, D.Graebling introduces thiuram compound in its patent US5569717, the free radical in the stabilising system.China applies for a patent CN200510117710, CN200610113313.3 and also discloses similar method.The structure of thiuram compound is as follows:
Wherein X is 1 or 2, R
1, R
2, R
3And R
4Alkyl or aryl for C atomicity 1-10.When patent US5569717 pointed out X=2, effect was better.For better control reaction, among the patent CN200710062451.8, when having used the auxiliary agent thiuram compound, in system, add organic clay, the formation of control branched structure has improved melt strength and mechanical property.Aspect polypropylene grafted modification, the activity of free radical in the system has been stablized in the adding of auxiliary agent thiuram compound, and obvious effects has been played in the raising of melt strength.In order further to widen the kind of auxiliary agent, save industrial cost, effectively improve polyacrylic melt strength, seek new free radical stabilizer, be the effective way of widening the preparation of industrialization high melt strength, propylene.
Summary of the invention
One of purpose of the present invention is to provide a kind of high bath strength acrylic resin and preparation method.It is restive and product gel content high and the problem of mechanical properties decrease that this high bath strength acrylic resin avoids introducing degradation of polypropylene that peroxide initiator causes.
This preparation method can improve polyacrylic melt strength, can better controlled react polyacrylic degraded in the free radical elicitation procedure again, also is difficult for producing gel when improving polypropylene grafted rate, and product melt blending, extrusion performance are had no adverse effects.
A kind of composition and consumption of high bath strength acrylic resin are as follows:
Polypropylene 100 weight parts,
Monomer 0.1～10 weight part that contains two keys, preferable amount 0.1～5 weight part,
Dithiocarbamate(s) material 0.001～1 weight part, preferable amount 0.01～0.5 weight part;
Described polypropylene, used polypropylene are ecosystem homopolymer or the multipolymer that does not add any auxiliary agent, preferred ecosystem homopolymer, and weight-average molecular weight is 50000～1500000g/mol, preferred 100000～600000g/mol; So-called ecosystem acrylic resin is meant the acrylic resin that does not add any auxiliary agent, come out by direct production in the polymeric kettle;
The described monomer that contains two keys can promote the combination between the polypropylene macromolecular radical as additional crosslinker, forms long branched chain structure.Regulate the polypropylene that its consumption and kind can make different branching and crosslinking degree.
The described monomer that contains two keys is the monomer that contains two two keys, contain the monomer of three two keys and contain in the monomer of four two keys one or more;
The described monomer that contains two two keys is selected from one or more in diacrylate and binary unsaturated olefin and the derivative thereof; In preferred methacrylate triglycol ester, two methyl TEG ester, 1,6 hexanediol diacrylate, neopentylglycol diacrylate, Vinylstyrene and the two toxilic acid two propylene esters one or more;
The described monomer that contains three two keys is selected from one or more in triacrylate and the triallyl, one or more in preferred Viscoat 295, ethoxylated trimethylolpropane triacrylate, propoxylation Viscoat 295 and the triallyl cyanurate.
The described monomer that contains four two keys is selected from one or more in the tetraacrylate, one or more in preferred tetramethylol methane tetraacrylate, tetramethylolmethane tetramethyl-acrylate and the ethoxylation tetramethylol methane tetraacrylate;
It is the effect of playing stabilized radical in the process of preparation branched p 0 lypropylene that used dithiocarbamate(s) auxiliary agent mainly acts on.In preparation process, the tertiary carbon macromolecular radical instability that polypropylene forms, at high temperature, do not have under the situation of dithiocarbamate(s) auxiliary agent, β-fracture plays a leading role, and causes degradation of polypropylene serious.And under the situation that the dithiocarbamate(s) auxiliary agent is arranged, free radical and polypropylene macromolecular radical that the dithiocarbamate(s) auxiliary agent produces are combined into a kind of inferior stable state product, and should react reversible, reduced the concentration of polypropylene macromolecular radical like this, suppressed β-fracture, thereby helped forming the branching type macromole with polyfunctional monomer.
The general formula of described dithiocarbamate(s) material is:
In the formula, R
1, R
2Be identical or different alkyl, cycloalkyl or aryl, R
1, R
2Alkyl, cycloalkyl heterocycle or the aryl of preferred C atomicity 1-10; M is metallic element, metallicity strong non-metallic element or non-metal cations; Described metallic element is Ni, Fe, Zn, Cu, Pb, Bi or Cd; The non-metallic element that described metallicity is strong is Te or Se; Described non-metal cations such as NH
4 +, [H
2NC
4H
10]
+
The preferred cupric dimethyldithiocarbamate of described dithiocarbamate(s), zinc-ethylphenyl dithiocarbamate, zinc diethyldithiocarbamate, ziram, zinc dibutyl dithiocarbamate or ferric dimethyl dithiocarbamate; More preferably cupric dimethyldithiocarbamate.
A kind of high bath strength acrylic resin and preparation method are as follows:
(1) fusion-grafting method: by proportioning the raw material that mixes is joined in 190～250 ℃ of Banbury mixeies, rotating speed is 20～120 rev/mins, and the reaction times is 1～15 minute, is mixed to moment of torsion discharging when constant; Perhaps, earlier polypropylene is joined in 190～250 ℃ of Banbury mixeies, after treating polypropylene fusion, add comonomer and dithiocarbamate(s), rotating speed is 20～120 rev/mins, reaction times is 1～15 minute, is mixed to moment of torsion discharging when constant, obtains a kind of high bath strength acrylic resin.
(2) fusion-grafting method: add in list or the twin screw extruder after with polypropylene, double bond containing monomer, the pre-mixing of dithiocarbamate(s) auxiliary agent by proportioning, 40～300 rev/mins of rotating speeds, list or twin screw extruder are 180～260 ℃ from the transportation section to the temperature of mouth mould, the reaction extruding pelletization obtains a kind of high bath strength acrylic resin.
Beneficial effect: the high melt strength, propylene of the present invention preparation, melt strength has improved twice to six times than raw material.The present invention adopts original position thermal initiation grafted method to prepare high bath strength acrylic resin.This method is simple, convenient, saves the cost in the production process, has improved high bath strength acrylic resin competitive power in market.The dithiocarbamate(s) auxiliary agent of this use and thiurams auxiliary agent relatively, action effect is good, can further reduce the consumption that contains double bond monomer, thereby further reduces the manufacturing cost of high melt strength, propylene.
The used major equipment of the present invention is Banbury mixer, single screw extrusion machine or twin screw extruder, and facility investment is few, and technology is simple, implements easily, and is with low cost.The products obtained therefrom melt strength obviously improves, and can be used for extrusion coated, thermoforming, foaming, blow-molded article.
Tensile strength (MPa) up to: 39; Tensile modulus (MPa) up to: 810;
Elongation at break (%) is: 738; Tc (℃) be: 113-225; Melting index (g/10min) is: 0.5-2.0; Melt strength (cN) is 16-36; Gel content (%) can reach 0.
The testing tool that the present invention adopts in an embodiment is as follows:
The tensile property test: adopt the Inxtron material experiment-machine, draw speed is 50mm/min;
Tc test: adopt DSC;
Melt index determination: adopt SRZ-400D type melt flow rate (MFR) determinator;
Melt strength is measured: adopt RHEOTENS 71.97 melt strength determinators.
Gel content (gel%): accurately take by weighing about polypropylene specimen 0.10g, wrap with 120 order copper mesh, weighing was soaked 12 hours in boiling xylene, dry back weighing.Gel content (gel%)=(soaking back residuals weight/former weight) * 100%.
Embodiment
Comparative example 1 (not adding ferric dimethyl dithiocarbamate)
Get 45g ecosystem powder (homo-polypropylene powder, melting index is 7.1g/10min), 0.05g Viscoat 295, in high-speed mixer, mix 20min, add in the material chamber of Banbury mixer, temperature is set at: 200 ℃, rotating speed: 80 rev/mins, moment of torsion is stablized discharging after 7 minutes reaction times.The results are shown in Table 1.
Embodiment 1 (adding ferric dimethyl dithiocarbamate)
Get 45g ecosystem powder (homo-polypropylene powder, melting index is 7.1g/10min), 0.05g Viscoat 295,0.02g ferric dimethyl dithiocarbamate, mix 20min in high-speed mixer, add in the material chamber of Banbury mixer, temperature is set at: 200 ℃, rotating speed: 80 rev/mins, moment of torsion is stablized discharging after 7 minutes reaction times.The results are shown in Table 1.
Comparative example 2 (not adding ferric dimethyl dithiocarbamate)
Polypropylene (homo-polypropylene powder with 100 weight parts, melting index is 7.1g/10min), 1.50 the Viscoat 295 of weight part mixes 20min. and joins L/D=40 in high-speed mixer, Φ is in the twin screw extruder of 24mm, the revolution of forcing machine is set at 240 rev/mins, forcing machine is divided into eight heating zone, be respectively: 175 ℃, 190 ℃, 200 ℃, 220 ℃, 230 ℃, 230 ℃, 230 ℃, 220 ℃, extruding pelletization obtains high bath strength acrylic resin.The results are shown in Table 1.
Embodiment 2 (adding ferric dimethyl dithiocarbamate)
Polypropylene (homo-polypropylene powder with 100 weight parts, melting index is 7.1g/10min), 0.20 the adding ferric dimethyl dithiocarbamate of weight part, 1.50 the Viscoat 295 of weight part mixes 20min. and joins L/D=40 in high-speed mixer, Φ is in the twin screw extruder of 24mm, the revolution of forcing machine is set at 240 rev/mins, forcing machine is divided into eight heating zone, be respectively: 175 ℃, 190 ℃, 200 ℃, 220 ℃, 230 ℃, 230 ℃, 230 ℃, 220 ℃, extruding pelletization obtains high bath strength acrylic resin.The results are shown in Table 1.
Embodiment 3
Get 45g ecosystem powder, (homo-polypropylene powder, melting index is 7.1g/10min) the 4.50g ethoxylated trimethylolpropane triacrylate, 0.06g cupric dimethyldithiocarbamate, mix 20min in high-speed mixer, add in the material chamber of Banbury mixer, temperature is set at: 210 ℃, rotating speed: 20 rev/mins, moment of torsion is stablized discharging after 7 minutes reaction times.The results are shown in Table 1.
Embodiment 4
Get 45g ecosystem powder, (homo-polypropylene powder, melting index is 7.1g/10min) 2.25g methacrylate triglycol ester, 0.1g zinc-ethylphenyl dithiocarbamate, mix 20min in high-speed mixer, add in the material chamber of Banbury mixer, the temperature that mixes is set at: 230 ℃, rotating speed: 60 rev/mins, moment of torsion is stablized discharging after 7 minutes reaction times.The results are shown in Table 1.
Embodiment 5
Get 45g ecosystem powder, (homo-polypropylene powder, melting index is 7.1g/10min) the two methyl TEG esters of 1.20g, 0.3g zinc diethyldithiocarbamate, mix 20min in high-speed mixer, add in the material chamber of Banbury mixer, temperature is set at: 250 ℃, rotating speed: 80 rev/mins, moment of torsion is stablized discharging after 7 minutes reaction times.The results are shown in Table 1.
Embodiment 6
Get 45g ecosystem powder, (homo-polypropylene powder, melting index is 7.1g/10min) the 0.60g tetramethylol methane tetraacrylate, 0.08g ziram, mix 20min in high-speed mixer, add in the material chamber of Banbury mixer, temperature is set at: 190 ℃, rotating speed: 120 rev/mins, moment of torsion is stablized discharging after 7 minutes reaction times.The results are shown in Table 1.
Embodiment 7
Polypropylene (homo-polypropylene powder with 100 weight parts, melting index is 7.1g/10min), 0.1 the triallyl cyanurate of weight part, mix 20min. and join L/D=40 in high-speed mixer, Φ is in the twin screw extruder of 24mm, and the revolution of forcing machine is set at 40 rev/mins, forcing machine is divided into eight heating zone, be respectively: 185 ℃, 210 ℃, 220 ℃, 220 ℃, 220 ℃, 220 ℃, 220 ℃, 210 ℃, extruding pelletization obtains high bath strength acrylic resin.The results are shown in Table 1.
Embodiment 8
Polypropylene (homo-polypropylene powder with 100 weight parts, melting index is 7.1g/10min), 0.01 the cupric dimethyldithiocarbamate of weight part, 0.50 the Viscoat 295 of weight part. in high-speed mixer, mix 20min. and join L/D=40, Φ is in the twin screw extruder of 24mm, the revolution of forcing machine is set at 80 rev/mins, forcing machine is divided into eight heating zone, be respectively: 185 ℃, 200 ℃, 200 ℃, 220 ℃, 220 ℃, 220 ℃, 230 ℃, 220 ℃, extruding pelletization obtains high bath strength acrylic resin.The results are shown in Table 1.
Embodiment 9
Polypropylene (homo-polypropylene powder with 100 weight parts, melting index is 7.1g/10min), 0.04 the zinc-ethylphenyl dithiocarbamate of weight part, 0.80 the propoxylation Viscoat 295 of weight part mixes 20min. and joins L/D=40 in high-speed mixer, Φ is in the twin screw extruder of 24mm, the revolution of forcing machine is set at 140 rev/mins, forcing machine is divided into eight heating zone, be respectively: 185 ℃, 200 ℃, 200 ℃, 220 ℃, 220 ℃, 230 ℃, 230 ℃, 220 ℃, extruding pelletization obtains high bath strength acrylic resin.The results are shown in Table 1.
Embodiment 10
Polypropylene (homo-polypropylene powder with 100 weight parts, melting index is 7.1g/10min), 0.60 weight part zinc dibutyl dithiocarbamate, 10 weight parts the ethoxylation tetramethylol methane tetraacrylate. in high-speed mixer, mix 20min. and put into L/D=40, Φ is in the twin screw extruder of 24mm, the revolution of forcing machine is set at 180 rev/mins, forcing machine is divided into eight heating zone, be respectively: 190 ℃, 220 ℃, 220 ℃, 220 ℃, 220 ℃, 220 ℃, 220 ℃, 220 ℃, extruding pelletization obtains high bath strength acrylic resin.The results are shown in Table 1.
Embodiment 11
Polypropylene (homo-polypropylene powder with 100 weight parts, melting index is 7.1g/10min), 0.40 the ziram of weight part, the ethoxylated trimethylolpropane triacrylate of 5 weight parts. in high-speed mixer, mix 20min. and join L/D=40, Φ is in the twin screw extruder of 24mm, the revolution of forcing machine is set at 160 rev/mins, forcing machine is divided into eight heating zone, be respectively: 185 ℃, 210 ℃, 210 ℃, 210 ℃, 220 ℃, 220 ℃, 230 ℃, 220 ℃, extruding pelletization obtains high bath strength acrylic resin.The results are shown in Table 1.
Embodiment 12
Polypropylene (homo-polypropylene powder with 100 weight parts, melting index is 7.1g/10min), 0.06 the zinc diethyldithiocarbamate of weight part, 1.20 the propoxylation Viscoat 295 of weight part. in high-speed mixer, mix 20min. and join L/D=40, Φ is in the twin screw extruder of 24mm, the revolution of forcing machine is set at 220 rev/mins, forcing machine is divided into eight heating zone, be respectively: 180 ℃, 200 ℃, 200 ℃, 220 ℃, 230 ℃, 230 ℃, 230 ℃, 220 ℃, extruding pelletization obtains high bath strength acrylic resin.The results are shown in Table 1.
Embodiment 13
Polypropylene (homo-polypropylene powder with 100 weight parts, melting index is 7.1g/10min), 0.05 the ferric dimethyl dithiocarbamate of weight part, 1.8 the methacrylate triglycol ester of weight part. in high-speed mixer, mix 20min. and join L/D=40, Φ is in the twin screw extruder of 24mm, the revolution of forcing machine is set at 150 rev/mins, forcing machine is divided into eight heating zone, be respectively: 180 ℃, 210 ℃, 230 ℃, 230 ℃, 230 ℃, 230 ℃, 230 ℃, 220 ℃, extruding pelletization obtains high bath strength acrylic resin.The results are shown in Table 1.
Embodiment 14
Polypropylene (homo-polypropylene powder with 100 weight parts, melting index is 7.1g/10min), 0.15 the cupric dimethyldithiocarbamate of weight part, the neopentylglycol diacrylate of 3 weight parts. in high-speed mixer, mix 20min. and join L/D=40, Φ is in the twin screw extruder of 24mm, the revolution of forcing machine is set at 190 rev/mins, forcing machine is divided into eight heating zone, be respectively: 180 ℃, 210 ℃, 230 ℃, 230 ℃, 230 ℃, 230 ℃, 230 ℃, 220 ℃, extruding pelletization obtains high bath strength acrylic resin.The results are shown in Table 1.
Embodiment 15
Polypropylene (homo-polypropylene powder with 100 weight parts, melting index is 7.1g/10min), 0.25 the zinc diethyldithiocarbamate of weight part, 3.5 the Viscoat 295 of weight part. in high-speed mixer, mix 20min. and join L/D=40, Φ is in the twin screw extruder of 24mm, the revolution of forcing machine is set at 210 rev/mins, forcing machine is divided into eight heating zone, be respectively: 180 ℃, 210 ℃, 230 ℃, 230 ℃, 230 ℃, 230 ℃, 230 ℃, 220 ℃, extruding pelletization obtains high bath strength acrylic resin.The results are shown in Table 1.
Embodiment 16
Polypropylene (homo-polypropylene powder with 100 weight parts, melting index is 7.1g/10min), 0.4 the zinc dibutyl dithiocarbamate of weight part, 2.5 the Vinylstyrene of weight part. in high-speed mixer, mix 20min. and join L/D=40, Φ is in the twin screw extruder of 24mm, the revolution of forcing machine is set at 300 rev/mins, forcing machine is divided into eight heating zone, be respectively: 180 ℃, 210 ℃, 230 ℃, 230 ℃, 230 ℃, 230 ℃, 230 ℃, 220 ℃, extruding pelletization obtains high bath strength acrylic resin.The results are shown in Table 1.
The test result of table 1. embodiment 1～16
| Sequence number | Tensile strength (MPa) | Tensile modulus (MPa) | Elongation at break (%) | Tc (℃) | Melting index (g/10min) | Melt strength (cN) | Gel content (%) |
| Virgin pp | ?38? | ?700? | 762? | 110? | 7.1? | 5? | 0? |
| The comparative example 1 | ?37? | ?720? | 730? | 115? | 1.8? | 9? | 0? |
| Embodiment 1 | ?38? | ?785? | 700? | 121? | 1.6? | 28? | 0? |
| The comparative example 2 | ?36? | ?770? | 720? | 116? | 2.0? | 10? | 0? |
| Embodiment 2 | ?38? | ?780? | 660? | 123? | 1.2? | 32? | 1.2? |
| Embodiment 3 | ?36? | ?760? | 690? | 119? | 1.2? | 22? | 0? |
| Embodiment 4 | ?36? | ?810? | 660? | 124? | 0.7? | 30? | 0? |
| Embodiment 5 | ?37? | ?780? | 680? | 122? | 0.9? | 25? | 0? |
| Embodiment 6 | ?38? | ?732? | 738? | 113? | 2.0? | 16? | 0? |
| Embodiment 7 | ?39? | ?770? | 675? | 120? | 0.7? | 25? | 0? |
| Embodiment 8 | ?38? | ?735? | 720? | 117? | 1.5? | 22? | 0? |
| Embodiment 9 | ?38? | ?810? | 650? | 125? | 0.5? | 36? | 1.30? |
| Embodiment 10 | ?36? | ?780? | 654? | 124? | 0.6? | 32? | 1.50? |
| Embodiment 11 | ?39? | ?783? | 660? | 124? | 0.6? | 33? | 0.80? |
| Embodiment 12 | ?38? | ?764? | 665? | 122? | 0.8? | 28? | 2.50? |
| Embodiment 13 | ?35? | ?780? | 667? | 123? | 0.8? | 30? | 0.70? |
| Embodiment 14 | ?36? | ?755? | 690? | 117? | 1.9? | 28? | 0.5? |
| Embodiment 15 | ?37? | ?770? | 670? | 120? | 1.6? | 34? | 1.5? |
| Embodiment 16 | ?38? | ?760? | 680? | 118? | 1.5? | 32? | 0.30? |
Claims (13)
1. a high bath strength acrylic resin is characterized in that, its component and consumption are as follows:
Polypropylene 100 weight parts,
Monomer 0.1～10 weight part that contains two keys,
Dithiocarbamate(s) material 0.001～1 weight part;
Described polypropylene, used polypropylene is not for adding the ecosystem homopolymer or the multipolymer of any auxiliary agent, and weight-average molecular weight is 50000～1500000g/mol; So-called ecosystem acrylic resin is meant the acrylic resin that does not add any auxiliary agent, come out by direct production in the polymeric kettle;
The monomeric consumption that contains two keys is 0.1～10 weight part;
The described monomer that contains two keys is the monomer that contains two two keys, contain the monomer of three two keys and contain in the monomer of four two keys one or more;
The described monomer that contains two two keys is selected from one or more in diacrylate and binary unsaturated olefin and the derivative thereof;
The described monomer that contains three two keys is selected from one or more in triacrylate and the triallyl;
The described monomer that contains four two keys is selected from one or more in the tetraacrylate;
Dithiocarbamate(s) is 0.001～1 weight part;
The general formula of described dithiocarbamate(s) material is:
In the formula, R
1, R
2Be identical or different alkyl, cycloalkyl or aryl; M is metallic element, metallicity strong non-metallic element or non-metal cations; Described metallic element is Ni, Fe, Zn, Cu, Pb, Bi or Cd; The non-metallic element that described metallicity is strong is Te or Se; Described non-metal cations is NH
4 +Or [H
2NC
4H
10]
+
2. a kind of high bath strength acrylic resin as claimed in claim 1 is characterized in that, described polypropylene is the ecosystem homopolymer.
3. a kind of high bath strength acrylic resin as claimed in claim 1 is characterized in that, described polypropylene is 100,000～600,000g/mol.
4. a kind of high bath strength acrylic resin as claimed in claim 1 is characterized in that, the described monomeric consumption that contains two keys is 0.1～5 weight part.
5. a kind of high bath strength acrylic resin as claimed in claim 1, it is characterized in that, the described monomer that contains two two keys is a methacrylate triglycol ester, 1, one or more in 6-hexanediyl ester, neopentylglycol diacrylate, Vinylstyrene and the two toxilic acid two propylene esters.
6. a kind of high bath strength acrylic resin as claimed in claim 1, it is characterized in that the described monomer that contains three two keys is selected from one or more in Viscoat 295, ethoxylated trimethylolpropane triacrylate, propoxylation Viscoat 295 and the triallyl cyanurate.
7. a kind of high bath strength acrylic resin as claimed in claim 1, it is characterized in that the described monomer that contains four two keys is selected from one or more in tetramethylol methane tetraacrylate, tetramethylolmethane tetramethyl-acrylate and the ethoxylation tetramethylol methane tetraacrylate.
8. a kind of high bath strength acrylic resin as claimed in claim 1 is characterized in that, described dithiocarbamate(s) is 0.01～0.5 weight part.
9. a kind of high bath strength acrylic resin as claimed in claim 1 is characterized in that, the R of the general formula of described dithiocarbamate(s) material
1, R
2Alkyl, cycloalkyl heterocycle or aryl for C atomicity 1-10; M is metallic element, metallicity strong non-metallic element or non-metal cations; Described dithiocarbamate(s) is a cupric dimethyldithiocarbamate.
10. a kind of high bath strength acrylic resin as claimed in claim 1, it is characterized in that described dithiocarbamate(s) is cupric dimethyldithiocarbamate, zinc-ethylphenyl dithiocarbamate, zinc diethyldithiocarbamate, ziram, zinc dibutyl dithiocarbamate or ferric dimethyl dithiocarbamate.
11. a kind of high bath strength acrylic resin as claimed in claim 10 is characterized in that, described dithiocarbamate(s) is a cupric dimethyldithiocarbamate.
12. the preparation method of a kind of high bath strength acrylic resin as claimed in claim 1, it is characterized in that, its step and condition are: by proportioning the raw material that mixes is joined in 190～250 ℃ of Banbury mixeies, rotating speed is 20～120 rev/mins, reaction times is 1～15 minute, is mixed to moment of torsion discharging when constant; Perhaps, earlier polypropylene is joined in 190～250 ℃ of Banbury mixeies, after treating polypropylene fusion, add comonomer and dithiocarbamate(s), rotating speed is 20～120 rev/mins, reaction times is 1～15 minute, is mixed to moment of torsion discharging when constant, obtains a kind of high bath strength acrylic resin.
13. the preparation method of a kind of high bath strength acrylic resin as claimed in claim 1, it is characterized in that, its step and condition are: add in list or the twin screw extruder after with polypropylene, double bond containing monomer, the pre-mixing of dithiocarbamate(s) auxiliary agent by proportioning, 40～300 rev/mins of rotating speeds, list or twin screw extruder are 180～260 ℃ from the transportation section to the temperature of mouth mould, the reaction extruding pelletization obtains a kind of high bath strength acrylic resin.
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| CN2008100516132A CN101434681B (en) | 2008-12-17 | 2008-12-17 | High melt strength acrylic resin and preparation |
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| CN103865176A (en) * | 2012-12-10 | 2014-06-18 | 中国石油天然气股份有限公司 | Preparation method of polypropylene with high melt strength |
| CN104592451A (en) * | 2015-01-09 | 2015-05-06 | 贵州大学 | High-grafting-ratio maleic anhydride graft polypropylene material and preparation method thereof |
| CN105924584B (en) * | 2016-05-15 | 2018-11-27 | 贵州大学 | Long chain branching high-density polyethylene material of resisting environmental stress and cracking and preparation method thereof |
| CN111019164B (en) * | 2019-12-18 | 2022-07-12 | 万华化学集团股份有限公司 | Method for testing proper crosslinking degree of molten polymer |
| WO2021133203A1 (en) * | 2019-12-27 | 2021-07-01 | Public Joint Stock Company "Sibur Holding" (Pjsc "Sibur Holding") | High melt strength polypropylene composition and process for manufacturing thereof |
| CN113024737A (en) * | 2021-04-07 | 2021-06-25 | 贵州大学 | Method for compatibilization of polypropylene/polyethylene blend |
| CN113896835B (en) * | 2021-10-27 | 2024-06-21 | 中国石油化工股份有限公司 | High melt strength polypropylene and preparation method and application thereof |
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