阅读说明：本技术 基于超临界流体的聚合物色母粒制备用色浆及其制备方法 (Polymer masterbatch standby color paste based on supercritical fluid and preparation method thereof ) 是由 严玉蓉 邹飞 于 2019-09-30 设计创作，主要内容包括：本发明公开了基于超临界流体的聚合物色母粒制备用色浆及其制备方法,属于色浆材料技术领域,其原料组分按照重量百分比计为：15～50％的色料,2～20％的超临界流体,0.1～10％的分散剂,0～20％的溶剂,0.01～10％的偶联剂,0.001～10％的氧化锌催化剂,0.001～10％的抗氧化剂,0.001～10％端基改性剂；本发明借助超临界流体优异的表面湿润能力,极高的扩散系数和低粘度系数,完成色料在色浆体系中的快速扩散与均匀分布,同时使用聚合物单体作为分散剂,实现色料在后续成型过程中的稳定分散。(The invention discloses the polymer masterbatch standby color pastes and preparation method thereof based on supercritical fluid, belong to mill base field of material technology, its raw material components is in percentage by weight are as follows: 15~50% colorant, 2~20% supercritical fluid, 0.1~10% dispersing agent, 0~20% solvent, 0.01~10% coupling agent, 0.001~10% Zinc oxide catalytic, 0.001~10% antioxidant, 0.001~10% terminal groups modification agent；The present invention surface wettability ability excellent by supercritical fluid, high diffusion coefficient and low viscosity coefficient, it completes quick diffusion of the colorant in colour paste system and is uniformly distributed, while using polymer monomer as dispersing agent, realize stable dispersion of colorant during subsequent forming.)

1. the polymer masterbatch standby color paste based on supercritical fluid, which is characterized in that its raw material components is according to weight hundred Ratio is divided to be calculated as: 15~50% colorant, 2~20% supercritical fluid, 0.1~10% dispersing agent, 0~20% solvent, 0.01~10% coupling agent, 0.001~10% Zinc oxide catalytic, 0.001~10% antioxidant, 0.001~ 10% terminal groups modification agent；

The terminal groups modification agent is the agent of toluene di-isocyanate(TDI) terminal groups modification, methyl diphenylene diisocyanate terminal groups modification Agent, the agent of lysine diisocyanate terminal groups modification and one of the sub- diamines terminal groups modification agent or a variety of that is carbonized；

The dispersing agent is polyamide 66 polymerized monomer, polymerization technology for polyamide 6 monomer, polycarbonate polymerization monomer, poly- methyl-prop E pioic acid methyl ester polymerized monomer, poly lactic acid polymerized monomer, polyethylene glycol polymeric monomer, polyoxyethylene polymerized monomer and polyethylene wax are poly- Close one of monomer or a variety of.

2. the polymer masterbatch standby color paste according to claim 1 based on supercritical fluid, it is characterised in that: institute The supercritical fluid stated is supercritical water or supercritical carbon dioxide.

3. the polymer masterbatch standby color paste according to claim 1 based on supercritical fluid, it is characterised in that: institute The colorant stated is one of cadmium sulfoselenide colorant, cerium sulphide colorant, zinc sulfur selenide colorant and tuscan red or a variety of.

4. the polymer masterbatch standby color paste according to claim 1 based on supercritical fluid, it is characterised in that: institute The coupling agent stated is 1- alkyl -3- methylimidazole type ionic liquid, 1- alkyl -2,3- methylimidazole type ionic liquid, ethylene Ethyl triethoxy silicane alkane coupling agent, vinyltrimethoxysilane coupling agent, distearyl acyl-oxygen isopropyl aluminate coupling agent, coke One of the phosphorous titanate coupling agent of phosphatic type titanate coupling agent, alkoxy and boric acid ester coupler are a variety of.

5. the polymer masterbatch standby color paste according to claim 1 based on supercritical fluid, it is characterised in that: institute The solvent stated is one of water, ethylene glycol, glycerine, polyamide 66 solution and polyamide 6 solution or a variety of.

6. the polymer masterbatch standby color paste according to claim 1 based on supercritical fluid, it is characterised in that: institute The antioxidant stated is phosphorous acid three (nonyl phenyl) ester antioxidant, N,N' diaryl p phenylene diamine antioxidant, thio two One of propionic acid antioxidant and magnesium alloy passivator are a variety of.

7. the preparation side of the polymer masterbatch standby color paste described in any one of claims 1-6 based on supercritical fluid Method, it is characterised in that: colorant and supercritical fluid are added in reaction kettle, stirred evenly, colorant is completely dissolved；Then Dispersing agent, solvent, coupling agent, Zinc oxide catalytic, antioxidant and terminal groups modification agent is added；It is again stirring for uniformly, reducing pressure Power makes supercritical fluid volatilize, and obtains the polymer masterbatch standby color paste based on supercritical fluid.

8. the preparation method of the polymer masterbatch standby color paste according to claim 7 based on supercritical fluid, Be characterized in that: the revolving speed stirred evenly for the first time is 600-800rpm, time 10-20min.

9. the preparation method of the polymer masterbatch standby color paste according to claim 7 based on supercritical fluid, Be characterized in that: the revolving speed stirred evenly for the second time is 300-500rpm, time 20-40min.

Technical field

The present invention relates to mill base field of material technology, and in particular to a kind of polymer masterbatch system based on supercritical fluid Standby color paste and preparation method thereof.

Background technique

Mill base, also known as color, i.e. pigment cooperate dispersing agent, the refined high concentration of the tool that takes this opportunity based on plasticizer Cream colored agent, be suitable for Toy Industry, silica gel medical equipment, PVC trade mark, silica gel trade mark, PVC artificial leather and EVA foamed products, Numerous industry fields such as acryl plate (organic glass).In general, mill base can be prepared there are many method, and such as: (1) colour mixture grind Mill: the various pigment of film-forming resin mixed grinding are used.This method have it is at low cost, the stable and uniform color development effect of quality it is excellent Point, but color accuracy is relatively low, and small lot is at high cost when producing, and the time of delivery can be limited.(2) color separation grind: at Film resin grinds traditional mill base preparation method of single pigment, this is current most popular method., small lot life stable with quality Convenient advantage when production.But this method requires mill base storage space big, and fixed cost consumption is high, and mill base milling time is long, hands over ETCD estimated time of commencing discharging can be also limited.(3) micro- rouge mill base: using resins for universal use, and preparation can apply to the high concentration mill base of multiple systems.It is this Method can save space, and small lot is flexible, at low cost when producing, the time of delivery is fast, while color shows.But resins for universal use Compatibility it is limited after all, and added a small amount of resin still will affect some performances of paint film, and the adjustment of formula is also very It is difficult.(4) resin-free color paste: dispersing agent and the direct ground pigment of solvent are used, almost all of resin system is applicable to.This Kind method has the institute of micro- rouge mill base advantageous, and avoids the defect of micro- rouge mill base, can be applied to most conventional Resin system, have high-quality, versatility, economy (high pigment loading) and be formulated easy to adjust, speed to respond to the market Fast advantage, but possible cost is slightly higher when mass production.

Pure material shows three kinds of solid phase, liquid phase, gas phase different conditions under different temperature and pressures.When temperature height When a certain value, no matter how high pressure, pure material all cannot be liquid phase by gas phase conversion, and it is to face that we, which define temperature at this time, Boundary's temperature (Tc)；And under corresponding critical-temperature, defining the minimum pressure that gas can be liquefied is critical pressure (Pc).Work as object The temperature of matter local environment is higher than critical-temperature, meanwhile, pressure is greater than critical pressure, which is at supercriticality.It is super Critical fluids are exactly the fluid of temperature and the equal postcritical of pressure.In Near The Critical Point, all physical property such as density of fluid is glued Variation sharply can occur for degree, dielectric constant, solubility, thermal capacity etc..Supercritical fluid is will not improving pressure Liquefied non-coherency gas, liquid phase are completely disappeared with gas phase boundary.

Chinese invention patent 2011104446817 discloses a kind of nano aqueous conductive carbon black color paste, comprising: conductive black 10.0~51.0%, powder dispersing agent 0.05~1.5%, coupling agent 0.5~2.5%, stabilizer 0.01~0.30%, water solubility Resin 0.1~2.0%, dispersing agent 1.0~7.0%, wetting agent 0.5~4.0%, anti-settling agent 0.01~0.3%, non-ionic emulsifier Agent 0.1~1.5%, pH adjusting agent 0.001~0.01%, deionized water 30~87%.The invention is mutually tied by physics with chemistry The method of conjunction prepares above-mentioned conductive carbon black color paste using dry grinding dispersion, dry surface modification and wet grinding technology；But Conductive black need by dry grinding and dry method modification and etc. control fineness, it is complicated for operation, modification degree be difficult to control, and And conductive black is as solid, it is difficult to guarantee effective evenly dispersed.

High fineness aqueous color paste and preparation method disclosed in Chinese invention patent 2011101044639 are for aqueous print Brush ink, weight percent composition are as follows: pigment 30~50%, aqueous dispersion 5~7%, aqueous defoamer 0.1-0.2%, Aqueous coupling agent 0.3~0.5% synthesizes wax emulsion 3~7%, and calcium carbonate superfine powder 3~5%, ultrafine kaolin 3~5%, it is heavy to resist Depressant prescription 3~5%, deionized water surplus；The invention is first to being dispersed in containing the granules of pigments in aqueous dispersion composition water phase It is ground, aqueous titanic acid ester coupling agent and synthesis wax emulsion is then added, at the high activity surface for the particle that is broken Manage and formed cladding, make its with can ultrafine particle is stable is dispersed in water-based system, obtain high fineness aqueous color paste；But water Property dispersing agent and polymer between there is a problem of it is incompatible, lotion dispersion process can occur demulsification reaction, may cause most Whole mill base can not stablize preservation.

Summary of the invention

It is not high for traditional colour paste colors material utilization rate, a large amount of contaminated wastewater environment are easy to produce, while solid additive needs Modification is wanted, subsequent dispersion is uneven, and dispersing agent and the bad problem of polymerization-filling object compatibility provide colorant in mill base body In system it is quick diffusion and be uniformly distributed, and realize stable dispersion of colorant during subsequent forming based on supercritical fluid Polymer masterbatch standby color paste.

The present invention in mill base by being added supercritical fluid, and using different polymer monomers as dispersing agent, and adds Add a certain amount of coupling agent, Zinc oxide catalytic, antioxidant and terminal groups modification agent, obtains a kind of poly- based on supercritical fluid Master batch standby color paste is looked in conjunction；The present invention surface wettability ability excellent by supercritical fluid, high diffusion coefficient and Low viscosity coefficient, complete colorant in colour paste system it is quick diffusion and be uniformly distributed, while use polymer monomer as divide Powder realizes stable dispersion of colorant during subsequent forming.

The object of the invention is achieved through the following technical solutions:

Polymer masterbatch standby color paste based on supercritical fluid, raw material components are in percentage by weight are as follows: 15~50% colorant, 2~20% supercritical fluid, 0.1~10% dispersing agent, 0~20% solvent, 0.01~10% Coupling agent, 0.001~10% Zinc oxide catalytic, 0.001~10% antioxidant, 0.001~10% terminal groups modification Agent；

The terminal groups modification agent is the agent of toluene di-isocyanate(TDI) terminal groups modification, methyl diphenylene diisocyanate end group changes Property agent, the agent of lysine diisocyanate terminal groups modification and one of the sub- diamines terminal groups modification agent or a variety of that is carbonized；

The dispersing agent is polyamide 66 polymerized monomer, polymerization technology for polyamide 6 monomer, polycarbonate polymerization monomer, poly- first Base methyl acrylate polymerized monomer, poly lactic acid polymerized monomer, polyethylene glycol polymeric monomer, polyoxyethylene polymerized monomer and polyethylene One of wax polymerized monomer is a variety of.

To further realize the object of the invention, it is preferable that the supercritical fluid is supercritical water or overcritical two Carbonoxide.

Preferably, the colorant is in cadmium sulfoselenide colorant, cerium sulphide colorant, zinc sulfur selenide colorant and tuscan red It is one or more.

Preferably, the coupling agent is 1- alkyl -3- methylimidazole type ionic liquid, 1- alkyl -2,3- dimethyl miaow Azoles type ionic liquid, vinyltriethoxysilane coupling agent, vinyltrimethoxysilane coupling agent, distearyl acyl-oxygen isopropyl In base aluminate coupling agent, pyrophosphoric acid type titanate coupling agent, the phosphorous titanate coupling agent of alkoxy and boric acid ester coupler It is one or more.

Preferably, the solvent is one of water, ethylene glycol, glycerine, polyamide 66 solution and polyamide 6 solution Or it is a variety of.

Preferably, the antioxidant is phosphorous acid three (nonyl phenyl) ester antioxidant, N, and N'- diaryl is to benzene two One of amine antioxidant, thio-2 acid antioxidant and magnesium alloy passivator are a variety of.

The preparation method of the polymer masterbatch standby color paste based on supercritical fluid, it is characterised in that: will Colorant and supercritical fluid are added in reaction kettle, are stirred evenly, and colorant is completely dissolved；Then be added dispersing agent, solvent, Coupling agent, Zinc oxide catalytic, antioxidant and terminal groups modification agent；It is again stirring for uniformly, reducing pressure waves supercritical fluid Hair, obtains the polymer masterbatch standby color paste based on supercritical fluid.

Preferably, the revolving speed stirred evenly for the first time is 600-800rpm, time 10-20min.

Preferably, the revolving speed stirred evenly for the second time is 300-500rpm, time 20-40min.

The present invention using different polymer monomers as dispersing agent, and is added by the way that supercritical fluid is added in mill base Coupling agent, Zinc oxide catalytic, antioxidant and terminal groups modification agent obtain a kind of polymer masterbatch based on supercritical fluid Standby color paste processed, by the surface wettability ability that supercritical fluid is excellent, high diffusion coefficient and low viscosity coefficient complete color Expect the quick diffusion in colour paste system and is uniformly distributed.Gas point is formed by using the discharge gasification of supercritical carbon dioxide Sub- extension further realizes the further dispersion of inorganic particle in mill base.Use polymer monomer as dispersing agent simultaneously, it is real Existing stable dispersion of colorant during subsequent forming.

Compared with prior art, the invention has the following advantages and beneficial effects:

(1) it is a discovery of the invention that supercritical fluid is added in mill base, it can use the excellent surface wettability of supercritical fluid Ability, high diffusion coefficient and low viscosity coefficient are completed quick diffusion of the colorant in colour paste system and are uniformly distributed.

(2) it has also been found that, first colorant is dissolved using supercritical fluid, then by supercritical fluid and solvent And other components mix jointly, using compatibility good between supercritical fluid and solution and mixed performance, may be implemented The Quick uniform of colorant disperses, and can remove supercritical fluid again finally by pressure is reduced.

(3) compatibility of dispersing agent and polymer is improved as dispersing agent by using polymer monomer, realizes that colorant exists Stable dispersion during subsequent forming；It is realized simultaneously by coupling agent, Zinc oxide catalytic, antioxidant and terminal groups modification agent Mill base is stabilized.

Specific embodiment

For a better understanding of the invention, the present invention will be further described with reference to the examples below, but reality of the invention It is without being limited thereto to apply mode.