KR20120115912A - Process for the preparation of polyvinyl chloride harde foam and polyvinyl chloride harde foam prepared therefrom - Google Patents

Abstract

PURPOSE: A manufacturing method of polyvinylchloride hard foam is provided to provide polyvinylchloride hard foam having excellent insulation, heat resistance, cold resistance, chemical resistance, self-extinguishing property, mechanical strength, etc. CONSTITUTION: A manufacturing method of polyvinylchloride hard foam comprises: a step of manufacturing a premix resin by mixing organic acid anhydride, reaction initiator, blowing agent AC#7000, a plasticizer dioctylphthalate, a vinylmonomer, BR-105, a secondary blowing agent n-pentane, TM-700R, B8462, polypropylene glycol and pigment, mixing polyvinylchloride into the premix resin, and mixing isocyanate into the mixture; a step of blowing the mixture on a press at 180 °C, and curing for 8 minutes; and a step of water-curing the cured material in water of 70-80 °C, and drying the cured material. [Reference numerals] (AA) PVC resin, organic anhydride acid, vinyl monomer, organic blowing agent, filler, etc; (BB) Isocyanate-based; (CC) Mixing; (DD) Input of mixing raw material; (EE) Manufacturing PLASTISOL due to an extruder; (FF) Raising temperature and pressurizing-molding; (GG) Oven; (HH) Blowing in oven; (II) Hydrating and blowing; (JJ) Water; (KK) Blowing agent; (LL) Product

Description

Process for preparing polyvinyl chloride rigid foam and polyvinyl chloride rigid foam prepared according to the present invention. PROCESS FOR THE PREPARATION OF POLYVINYL CHLORIDE HARDE FOAM AND POLYVINYL CHLORIDE HARDE FOAM PREPARED THEREFROM

The present invention relates to a process for preparing polyvinyl chloride (PVC) rigid foams and to PVC rigid foams prepared accordingly.

In terms of efficient use and saving of energy, the development and effective use of thermal insulation materials is also very important. Currently, heat insulating materials are largely classified into organic polymer resins and inorganic resins, and their methods of use vary according to their physical properties and properties. In general, while organic insulating material has better heat insulation, light weight, water resistance, processability, and impact resistance than inorganic heat insulating material, heat resistance or durability is inferior. Therefore, when a multi-functional insulating material complementary to each characteristic is developed, the limitation of the use range can be greatly alleviated, and new applications are possible. Crosslinkable PVC Rigid Foam is a new functional insulation material with much higher heat resistance, low temperature resistance, chemical resistance, and mechanical strength in addition to the general properties of organic insulation, and is evaluated as PVC organic insulation material that can fully function in a wider range of harsh conditions. have. In particular, the crosslinkable PVC rigid foam has excellent properties such as mechanical strength, self-extinguishing, heat resistance, as well as the characteristics of the existing organic foam. Therefore, these properties enhance the competitiveness of crosslinkable PVC rigid foams over existing organic foams, and are widely used as a single structural material in industries such as housing, construction, refrigeration, refrigeration, LNG storage tanks, aircraft, and ships. It is a product that is continuously expanding its scope of use as the use continues to be developed. In other words, PVC rigid foam is a high performance insulation suitable for special applications beyond the scope of conventional universal insulation.

In view of the efficient use and saving of energy, the development of excellent insulation materials and the establishment of effective utilization methods are very important. The use of organic foam as a thermal insulation material has played an essential role in related industrial and architectural construction, such as efficient use and saving of energy, weight reduction of structures, and noise shielding, but the range of use is inevitable depending on the required use. .

Insulation technology using foams has been widely used until now, but where thermal insulation materials excellent in mechanical strength, heat insulation, low permeability of water vapor and gas, low temperature resistance, chemical resistance, self-extinguishing, and workability are required, Usage restrictions are inevitable. Foams with various uses are used in building structures and partition panels that require self-extinguishing and mechanical strength. Cores, lining materials, or refrigeration and refrigeration equipment in vehicles, ships and aircrafts that require heat insulation, self-extinguishing and high mechanical strength. It is very useful for heat insulation.

Foams using vinyl chloride resin include PVC soft foams and crosslinkable PVC rigid foams. Soft PVC foam is used in automobile interiors, carpets, artificial leather and the like, crosslinkable PVC rigid foam is a foam that complements the disadvantages of the recent polyurethane foam, polystyrene foam and the like. The crosslinkable PVC rigid foam has been produced by KRP of France, and many products have been used in various countries around the world. The manufacturing method includes KRP No. and LONZA method. Products manufactured by LONZA method are semi-rigid or soft foams. First of all, KRP method is manufactured by four types of processes: PVC paste resin, foam hardening and finishing process under heating pressure, and other methods are made of plastisol using PVC paste resin, isocyanates, organic solvents, foams, etc. as raw materials. It is produced by five steps of removing, curing and finishing the expanded organic solvent under heating and pressing.

In particular, PVC rigid foams with a heat-resistant temperature ranging from -195 ° C to 90 ° C are optimal for cryogenic pipelines, LNG, LPG storage and refrigeration, but are slightly lower than other insulations in terms of cost. Although the production process has been improved, the development process has been steadily being improved, the continuous development has been made in terms of the use development, and the production process of the rigid PVC foam is being simplified. It was used.

The production of crosslinkable PVC rigid foams with excellent mechanical strength as well as good thermal and numerical stability began to be introduced in Europe in the early 1960s on the basis of Kleber-Colombes' patent using a reactive plasticizer system.

Crosslinkable PVC rigid foams were introduced in Europe in 1963 based on a patent by Kleber-Colombes. The foam has excellent mechanical properties and excellent thermal insulation, and has been actively commercialized. Currently, the foams are based on KRP in France, and are based on the company's unique characteristics from PERMAKI in the UK, LONZA in Switzerland, KIAB in Sweden, and SEREX in the USA. It is manufactured by the method.

Rigid PVC foam has a very small change in thermal conductivity due to the increase in density, so high-density products for high loads are expected to serve as excellent thermal insulators, and also have low thermal expansion coefficients, which can provide reliability as a precision material. The least deformation under high temperature and high humidity conditions and organic solvents, and flame retardancy PVC which is important as a building material is superior to other organic foams. In summary, it can be seen that the crosslinkable PVC rigid foam is a multifunctional foam having various characteristics and superiorities not expected from conventional general organic foams.

The process for producing a crosslinkable PVC rigid foam consists of plastisol preparation, pressure under high temperature and high pressure, stress relaxation in an oven and foaming and curing with hot water or steam. Nucleation of bubbles occurs during the high-pressure molding process, and immediately after demolding, the expansion rate is expanded to a certain size according to the density standard. Stress relaxation and hydration give foams with a specific gravity of 0.25-0.03 g / cm 3, depending on the density specifications. The anhydride acts as a plasticizer for the reactive PVC during the molding process and becomes unplasticized as the anhydride turns into diacid during foaming under high humidity. The raw material composition of the Kleber-Colombes foam is PVC, isocyanates, monomers, anhydrides, polymerization catalysts, freons, etc. The mixing of each component is mixed using a werner-type internal mixer or the like. The mixed plastitol is molded at 180-200 under a suitable pressure. As the polymerization reaction of the monomers and anhydride proceeds to generate heat and rises to about 80, the temperature must be lower than the actual reaction temperature.

Due to these reasons and the manufacturing conditions according to the standard, the composition of the monomer anhydride and other additives is very important. Preforms with demolded flexibility, when treated with hot water or steam, undergo water vapor penetration and foaming reactions to cure, creating a more expanded final cured foam. This foam is a PVC rigid foam that is modified by thermosetting or solvent insoluble through grafting and crosslinking of reactive plasticizers and additives, which is thermoplastic PVC, when polystyrene foam or polyethylene foam, which is a general thermoplastic foam, is left for 90 to 200 hours. While shrinkage is more than 65%, the heat shrinkage rate is less than 5%, and it has thermal insulation and self-extinguishing which is important as a heat insulator.

Cross-linkable PVC rigid foam is a kind of multifunctional structural insulation material that can alleviate the unavoidable limitation of use due to the lack of performance of existing general-purpose foams. It is particularly excellent in heat insulation, heat resistance, cryogenic resistance, chemical resistance, self-extinguishing and mechanical strength. It is evaluated. These properties make them useful for a wide range of insulating building materials, refrigeration equipment and aircraft, interior linings of vehicles, and the inner core of various composite materials. In particular, cryogenic insulation up to -195 ℃ is superior to any organic thermal insulation material, and has been proven to be used in the insulation of liquefied natural gas, liquefied petroleum gas storage tanks and pipelines. Therefore, the research and development of crosslinkable PVC rigid foam, which is expected to be highly functionalized, highly efficient and diversified, is considered to have great significance in view of the domestic development and the ripple effect in related fields.

An object of the present invention is to provide a method for producing a PVC rigid foam.

Another object of the present invention is to provide a PVC rigid foam prepared according to the above production method.

In order to achieve the above object, the present invention provides a method for producing a polyvinyl chloride (PVC) rigid foam comprising the following steps:

(1) 3 to 8 parts by weight of organic acid anhydride, 1 part by weight of reaction initiator, 4 to 8 parts by weight of AC # 7000 blowing agent, 28 parts by weight of plasticizer dioctylphthalate, 4 parts by weight of vinyl monomer, 2 parts by weight of BR-105, 2 2-5 parts by weight of the primary blowing agent n-pentane, 2 parts by weight of TM-700R, 0.06 parts by weight of B8462, 11 parts by weight of polypropylene glycol and 1.3 parts by weight of a pigment were mixed to prepare a premix resin, followed by polyvinyl chloride (PVC ) 100 parts by weight of the mixture, and then 70 parts by weight of isocyanate and mixing for 1 minute;

(2) foaming the mixture obtained in the above step at 180 ° C. on a press and then curing for 8 minutes; And

(3) curing the cured product obtained in the above step in water of 70 to 80 ° C. and then drying for 24 hours.

In order to achieve the above another object, the present invention provides a PVC rigid foam prepared according to the production method.

PVC rigid foam according to the present invention is a kind of multi-functional structural insulation material that the conventional general-purpose foam can alleviate the unavoidable use restrictions due to the lack of performance of insulation, heat resistance, cryogenic resistance, chemical resistance, self-extinguishing and mechanical strength The back light is particularly good, which makes it useful for a wide range of insulating building materials, refrigeration equipment and interior linings of aircraft vehicles, and interior cores of various composite materials. In particular, in the cryogenic insulation up to -195 ℃, it is much superior to any organic insulating material, and the performance is excellent when used for the insulation of liquefied natural gas, liquefied petroleum gas storage tanks and pipelines. Therefore, the PVC foam of the present invention is expected to be very useful for high functionalization and diversification of the insulation system.

Figure 1 shows the manufacturing process of the PVC rigid foam of the present invention.
2 shows the foam spectrum according to the amount of maleic anhydride added.
Figure 3 shows the foam spectrum according to the addition amount of n-pentane.
4 shows the foam spectrum according to the amount of phthalic anhydride added.
5 shows a foam spectrum according to the amount of polypropylene glycol added.
6 to 9 show SEM pictures of the PVC foam prepared in Examples 1 to 4.
10 to 13 show SEM pictures of the PVC foams prepared in Examples 5 to 8.
14 to 17 show SEM pictures of the PVC foams prepared in Examples 9 to 12.
18 to 21 show SEM pictures of the PVC foams prepared in Examples 13 to 16.
22 to 25 show SEM pictures of the PVC foam prepared in Examples 17 to 20.
26 to 29 show SEM pictures of the PVC foam prepared in Examples 21 to 24.
30 to 33 show SEM pictures of the PVC foam prepared in Examples 25 to 28.
34 to 38 show SEM pictures of the PVC foam prepared in Examples 29 to 33.
39 to 42 show SEM pictures of the PVC foams prepared in Examples 34 to 37.
43 to 46 show SEM pictures of the PVC foams prepared in Examples 42 to 45.
47 to 50 show SEM pictures of the PVC foam prepared in Examples 46 to 49.
51 to 55 show SEM pictures of the PVC foams prepared in Examples 50 to 54.
56 to 59 show SEM pictures of the PVC foam prepared in Examples 55 to 58.
60 to 63 show SEM pictures of the PVC foams prepared in Examples 59 to 62.

The technical terms and scientific terms used in the present invention can be construed as meaning ordinary meanings understood by those of ordinary skill in the art without departing from the scope of the present invention.

Method for producing PVC of the present invention (1) 3 to 8 parts by weight of an organic acid anhydride, 1 part by weight of reaction initiator, 4 to 8 parts by weight of blowing agent AC # 7000, 28 parts by weight of plasticizer dioctylphthalate, 4 parts by weight of vinyl monomer, BR-105 2 parts by weight, 2 to 5 parts by weight of the secondary blowing agent n-pentane, 2 parts by weight of TM-700R, 0.06 part by weight of B8462, 11 parts by weight of polypropylene glycol and 1.3 parts by weight of pigment were mixed for 1 minute. Preparing and mixing 100 parts by weight of polyvinyl chloride (PVC), and then adding 70 parts by weight of isocyanate and mixing for 1 minute; (2) foaming the mixture obtained in the above step at 180 ° C. on a press and then curing for 8 minutes; And (3) curing the cured product obtained in the above step in water at 70 to 80 ° C. and then drying for 24 hours.

Unlike general PVC processing conditions, the PVC production method of the present invention involves a chemical reaction during the molding process and is manufactured through several steps. This manufacturing process is largely composed of four steps, such as the production of plastisol by extrusion, foaming under heating pressure, foam hardening, finishing process, each step is as follows.

First Step: Plastisol Preparation by Extrusion

This step of the plastisol manufacturing process is the most important process in which the physical properties of the final PVC rigid foam and the density of the foam are determined. PVC plastics, foams, isocyanates, fillers, vinyl monomers, organic anhydrides, and the like are mixed with other additives to prepare PVC plastisols. The amount of each component has a decisive influence on the specification of the PVC rigid foam, and the mechanical strength, thermal conductivity, thermal stability, chemical resistance, and foam cell size can be adjusted according to the density. The plastisol can be prepared by extrusion of the raw materials before extrusion. Usually, homogeneous production of plastisols first requires uniform powder mixing of PVC resins, foams, fillers and the like. Secondly, isocyanates, vinyl monomers, organic anhydrides, etc., are prepared by mixing plastitols.The preparation temperature should be maintained at a temperature of 25-30 ℃ to prevent viscosity rise. This will continue until a homogeneous plastisol is obtained, but usually laboratory conditions are sufficient for 10-20 minutes.

Second Step: Foaming Under Warming Pressure

The prepared plastisol is put into a mold and gelled by heating under high pressure with a hot press, and at the same time, fine bubbles are formed by a decomposition reaction of the blowing agent. In this process, PVC resin and various reactive additives are grafted to each other, and after cooling under pressure, demolding gives a flexible PVC pre-foam.

Third step: foam hardening process

When the flexible PVC pre-foam is treated with hot water or steam, the foaming proceeds further by the decomposition reaction of the secondary blowing agent, and at the same time, a crosslinking reaction occurs to harden the inside to obtain a final foam.

Fourth step: finishing process

The prepared crosslinkable PVC foam is cut according to various standards or shipped to the product after surface treatment by heat.

The most basic chemical reaction mechanisms of the foam of the present invention include primary and secondary foaming with a foaming initiator and three-dimensional crosslinking by crosslinking reaction of a reactive additive. Through this reaction, various density control and physical property change can be given, and density control by use is also possible.

In the process of gelling the plastisol upon heating under high pressure, primary foaming is performed by thermal decomposition of a thermally decomposable blowing agent, and radical grafts such as vinyl acetate monomer and phthalic anhydride, which are monomers, occur.

The reaction mechanism is a soft pre-foamed foam after high-pressure molding is a graft polymer state and easily dissolved by PVC solvents such as dimethylformamide.However, when the secondary foaming and crosslinking reaction is completed by steam treatment, it is cured as three-dimensional crosslinking. Insoluble in organic solvents and the like. The crosslinked structure by blending with polypropylene glycol in the structure of the existing PVC improves chemical resistance and mechanical properties.

On the other hand, the crosslinking reaction is carried out by the amide bond reaction of the organic anhydride and polyamine grafted to the PVC carbon chain and the reaction is carried out by secondary foaming and crosslinking reaction.

Polyamines are produced with CO ₂ when the polyisocyanate reacts with water. Therefore, the secondary foaming is made by the generation of CO ₂ , to form a cured foam modified with a high molecular compound of a polymer network structure of the PVC chain crosslinked by an amide bond. 1 shows the overall process diagram of the production of the reaction.

PVC paste resins, isocyanates, vinyl monomers, anhydrides, blowing agents, fillers, organic solvents, and the like are mixed and used to prepare the final PVC rigid foam. Types and characteristics of each component are as follows.

In the foam of the present invention, PVC resin is used as a main component, PVC resin is largely divided into a straight line and a paste, and for the purpose of this study, the paste resin used in the production of plastisol was mainly studied. PVC resin used in the present invention was used to purchase a number of domestic products. As many kinds of PVC resins as possible are obtained, the optimum PVC resins are selected, but the range of viscosity, gelation time, molecular weight, etc. of the plastitol should be determined according to the overall manufacturing process. Was selected. PE1311 is a homopolymer made from emulsion polymerization, a high-viscosity PVC resin with flow properties similar to plastics in the processing range, suitable for thick foams.

Toluene diisocyanate, methylene diphenyl diisocyanate, polymethylene diphenyl diisocyanate, etc. are mainly used as an isocyanate used by this invention. They do not participate in the reaction at all until the high-pressure molding process, and the first curing product reacts with water to produce polyamine and CO ₂ , and the second polyamine reacts with anhydride to form an amide bond. To be At this time, the isocyanate group has the most crosslinked structure, and the shorter the crosslinking distance, the better the rigidity of the foam and the thermal characteristics are improved, while the impact resistance and flexibility are worsened. In addition, the physical properties of the foam changes the blending ratio, blending composition according to the type of isocyanate, and also changes the physical properties. Therefore, TDI-80, the largest producer of toluene diisocyanate (TDI) in Korea, was selected and tested.

Organic acids used in the present invention are unsaturated organic acids, such as maleic anhydride, phthalic anhydride, and the like, which form a PVC graft copolymer like vinyl monomers, and have an anhydride reactor capable of generating an amide bond with a polyamine during hydration curing. Phthalic anhydride was evaluated as having no problems in the physical properties of the final product while being easy to supply and use in Korea as a main component of the foam of the present invention. In the prior meaning, it is an anhydride of phthalic acid, a colorless needle-like crystal, industrially produced by oxidizing naphthalene or ortho xylene in the gas phase using vanadium pentoxide as a catalyst, and is mainly used as a plasticizer of plastics. Also called phthalic anhydride or phthalic anhydride (molecular formula C8H4O3). It is a colorless acicular crystal with a peculiar smell. It has a molecular weight of 148.12, melting point of 131 ℃, and boiling point of 285 ℃. It is sublimable. It has a structure in which one molecule of water is released from two carboxyl groups-COOH in a phthalic acid molecule. Slightly soluble in water, slowly hydrolyzed to phthalic acid. Slightly soluble in ether Phthalic anhydride can be obtained by heating and dehydrating phthalic acid, but industrially, it is prepared by oxidizing naphthalene or ortho xylene in a gas phase using vanadium pentoxide V2O5 as a catalyst. It is used as a plasticizer for plastics and also as a raw material for producing alkyd resin phenolphthalein dyes.

The vinyl monomer used in the present invention is a radically polymerizable monomer such as styrene, acrylonitrile, methyl methacrylate, vinyl acetate, vinylpyridine, etc., together with the decomposition of the blowing agent and the initiator to cause graft polymers on the PVC chain and maleic anhydride, etc. Copolymerization with the organic anhydride proceeds, and effective crosslinking occurs during the hydration curing reaction, thereby enabling structural modification. The physicochemical properties of the monomers are somewhat related to the final product and need to be selected in consideration of the ease of supply and demand of domestic raw materials, economic aspects and physical property control.

The organic blowing agent used in the present invention releases nitrogen or oxygen gas while being decomposed by heat, but when uniform dispersion and foaming are not performed, the homogeneity of the manufactured product through secondary foaming and curing is not guaranteed. Therefore, in the present invention, many foaming agents supplied in Korea were obtained and the foams were produced under various conditions. In order to obtain a uniform foam, a partial foaming reaction should not occur, and foaming is induced at a desired time, thereby forming a uniform cell distribution and size. In order to satisfy these conditions, it is necessary to control the decomposition temperature, decomposition rate, etc. of the blowing agent, and it is necessary to select a blowing agent that can meet the manufacturing conditions such that the specimen does not decompose before reaching the proper temperature and pressure. The resulting manufacturing conditions were also inferred.

In addition, fillers are generally used to reduce the cost of raw materials, but are used for other purposes in the present invention. It is meaningful to control the flow properties of plastisols, and also serves as a secondary blowing agent and also as a stabilizer for the cell. It also helps physical properties such as heat resistance, dimensional stability and impact resistance of foams. Some of the fillers may also be used to neutralize and ionic crosslink the rigid PVC foam final resin.

The volatile liquid blowing agent used in the present invention is a blowing agent that forms bubbles by pouring into a molten resin in a gas or a liquid and then volatilizing at a boiling point. In the case where the foam is manufactured with methirendiphenyl diisocyanate (MDI), which is a secondary blowing agent, the foam product can be manufactured by slightly changing the composition, such as manufacturing conditions, but in the low density foam product, sufficient foaming is difficult with the chemical foaming agent alone. In addition, it can be prepared by adding a large amount of other additives, such as an organic foaming agent, but the use of physical blowing agents is required because the economical efficiency and optimum conditions of the additives are limited. Freon foams are usually used, but for the sake of simplicity, the present invention mainly used inexpensive dichloroethane or volatile hydrocarbons for relatively easy and inexpensive control of the desired density.

In general, PVC rigid foam is often used as an exterior material in terms of application, and in most cases, colorant needs to be added. In the present invention, a powder pigment is used as a pigment, which preferably has a medium viscosity, and is currently commercially available in the form of a pigment-plasticizer-resin as a dry powder from a producer and is easily dispersed in a plastisol. The addition amount is usually preferably less than 1% of the PVC powder resin according to the standard density. In this study, various pigments were obtained and the coloration experiments resulted in satisfactory products.

Hereinafter, the present invention will be described in more detail with reference to Examples and Test Examples. However, the following Examples and Test Examples are only for illustrating the present invention, and the scope of the present invention is not limited only to these Examples and Test Examples.

Example  One

3 to 8 parts by weight of organic acid anhydride, 1 part by weight of azoisobutylonitrile as a reaction initiator, 6 parts by weight of foaming agent AC # 7000, 28 parts by weight of plasticizer dioctylphthalate, 4 parts by weight of styrene, 2 parts by weight of BR-105, 2 4 parts by weight of primary blowing agent n-pentane, 2 parts by weight of TM-700R, 0.06 part by weight of B8462, 11 parts by weight of polypropylene glycol 400 and 1.3 parts by weight of pigment were prepared for 1 minute to prepare a premix resin, followed by polyvinyl chloride (PVC) After adding 100 parts by weight of the mixture, 70 parts by weight of isocyanate was added and mixed for 1 minute.

The container used was a mixing device, a defoaming device, and a manufacturing temperature maintaining device.

(Step 2) High pressure molding

Filling 100g PVC plastisol prepared in step 1 into a mold of 10cm × 10cm × 2.5cm, sealed, pressurized by a press and maintained for 8 minutes at a molding temperature of 180 ℃ and the reaction of gelation, graft, micro-cell formation And structural change occurred. After the reaction, the mixture was cooled to 75 ° C. and demolded. Leaving the demolded soft foam in a 110 ° C. oven allowed the internal stresses to relax to form a balanced foam. The manufacturing conditions may vary depending on the composition of the plastisol, the size of the mold, etc., but there is no significant difference.

(Step 3) Hydration Reaction

The prepared pre-foam was left in a hot bath of about 100 ℃ (70 to 80 ℃) for about 24 hours and then hydrated. The hydration reaction reacted with isocyanate and water in the plastisol, and the microcell of the flexible foam became larger due to the generation of CO ₂ gas, and amide crosslinking occurred due to the reaction between the grafted anhydride and the isocyanate, causing curing. Therefore, during the hydration reaction, the reaction temperature affects the density of the product. Cured foams must be fully cured and the curing reaction rate must be fast for economic reasons. The reaction time should be dependent on the density of the product by regulation and the thickness of the cured foam should also be determined at an appropriate level because the thicker the final product of the foam, the slower the internal curing reaction.

Example  2 to 4

A foam was prepared in the same manner as in Example 1 except that the amount of phthalic anhydride added was changed as shown in Table 1 below. 6 to 9 show SEM pictures of the PVC foams prepared in Examples 1 to 4 above.

Experiment (g)
Raw material Example 1 Example 2 Example 3 Example 4 PVC 100.0 100.0 100.0 100.0 MDI 70.0 70.0 70.0 70.0 PA 4.0 5.0 6.0 7.0 AIBN 1.0 1.0 1.0 1.0 AC # 7000 6.0 6.0 6.0 6.0 DOP 28.0 28.0 28.0 28.0 Styrene 4.0 4.0 4.0 4.0 BR-105 2.0 2.0 2.0 2.0 n-Pentane 4.0 4.0 4.0 4.0 TM-700R 2.0 2.0 2.0 2.0 B8462 0.06 0.06 0.06 0.06 PPG 400 11.0 11.0 11.0 11.0 Pigment 1.3 1.3 1.3 1.3

Example  5 to 8

A foam was prepared in the same manner as in Example 1 except that the amount of the blowing agent AC # 7000 was changed as shown in Table 2 below. 10 to 13 show SEM pictures of the PVC foams prepared in Examples 5 to 8.

Experiment (g)
Raw material Example 5 Example 6 Example 7 Example 8 PVC 100.0 100.0 100.0 100.0 MDI 70.0 70.0 70.0 70.0 PA 6.0 6.0 6.0 6.0 AIBN 1.0 1.0 1.0 1.0 AC # 7000 4.0 5.0 6.0 7.0 DOP 28.0 28.0 28.0 28.0 Styrene 4.0 4.0 4.0 4.0 BR-105 2.0 2.0 2.0 2.0 n-Pentane 4.0 4.0 4.0 4.0 TM-700R 2.0 2.0 2.0 2.0 B8462 0.06 0.06 0.06 0.06 PPG 400 11.0 11.0 11.0 11.0 Pigment 1.3 1.3 1.3 1.3

Example  9-12

A foam was prepared in the same manner as in Example 1 except that the amount of n-pentane added was changed as shown in Table 3 below. 14 to 17 show SEM pictures of the PVC foams prepared in Examples 9 to 12.

Experiment (g)
Raw material Example 9 Example 10 Example 11 Example 12 PVC 100.0 100.0 100.0 100.0 MDI 70.0 70.0 70.0 70.0 PA 6.0 6.0 6.0 6.0 AIBN 1.0 1.0 1.0 1.0 AC # 7000 6.0 6.0 6.0 6.0 DOP 28.0 28.0 28.0 28.0 Styrene 4.0 4.0 4.0 4.0 BR-105 2.0 2.0 2.0 2.0 n-Pentane 2.0 3.0 4.0 5.0 TM-700R 2.0 2.0 2.0 2.0 B8462 0.06 0.06 0.06 0.06 PPG 400 11.0 11.0 11.0 11.0 Pigment 1.3 1.3 1.3 1.3

Example  13 to 16

A foam was prepared in the same manner as in Example 1 except that the amount of pyromellitic anhydride added was changed as shown in Table 4 below. 18 to 21 show SEM pictures of the PVC foams prepared in Examples 13 to 16.

Experiment (g)
Raw material Example 13 Example 14 Example 15 Example 16 PVC 100.0 100.0 100.0 100.0 MDI 70.0 70.0 70.0 70.0 PMDA 4.0 5.0 6.0 7.0 AIBN 1.0 1.0 1.0 1.0 AC # 7000 6.0 6.0 6.0 6.0 DOP 28.0 28.0 28.0 28.0 Styrene 4.0 4.0 4.0 4.0 BR-105 2.0 2.0 2.0 2.0 n-Pentane 4.0 4.0 4.0 4.0 TM-700R 2.0 2.0 2.0 2.0 B8462 0.06 0.06 0.06 0.06 PPG 400 11.0 11.0 11.0 11.0 Pigment 1.3 1.3 1.3 1.3

Example  17 to 20

A foam was prepared in the same manner as in Example 1 except that the amount of maleic anhydride added was changed as shown in Table 5 below. 22 to 25 show SEM pictures of the PVC foams prepared in Examples 17 to 20.

Experiment (g)
Raw material Example 17 Example 18 Example 19 Example 20 PVC 100.0 100.0 100.0 100.0 MDI 70.0 70.0 70.0 70.0 MA 4.0 5.0 6.0 7.0 AIBN 1.0 1.0 1.0 1.0 AC # 7000 6.0 6.0 6.0 6.0 DOP 28.0 28.0 28.0 28.0 Styrene 4.0 4.0 4.0 4.0 BR-105 2.0 2.0 2.0 2.0 n-Pentane 4.0 4.0 4.0 4.0 TM-700R 2.0 2.0 2.0 2.0 B8462 0.06 0.06 0.06 0.06 PPG 400 11.0 11.0 11.0 11.0 Pigment 1.3 1.3 1.3 1.3

Example  21 to 24

A foam was prepared in the same manner as in Example 1, except that the polypropylene glycol had a molecular weight of 1,000 and the phthalic anhydride addition amount was changed as shown in Table 6 below. 26 to 29 show SEM pictures of the PVC foams prepared in Examples 21 to 24.

Experiment
Raw material Example 21 Example 22 Example 23 Example 24 PVC 100.0 100.0 100.0 100.0 MDI 70.0 70.0 70.0 70.0 PA 3.0 4.0 5.0 6.0 AIBN 1.0 1.0 1.0 1.0 AC # 7000 6.0 6.0 6.0 6.0 DOP 28.0 28.0 28.0 28.0 Styrene 4.0 4.0 4.0 4.0 BR-105 2.0 2.0 2.0 2.0 n-Pentane 4.0 4.0 4.0 4.0 TM-700R 2.0 2.0 2.0 2.0 B8462 0.06 0.06 0.06 0.06 PPG 1000 11.0 11.0 11.0 11.0 Pigment 1.3 1.3 1.3 1.3

Example  25 to 28

A foam was prepared in the same manner as in Example 1 except that the polypropylene glycol had a molecular weight of 1,000 and the amount of maleic anhydride added was changed as shown in Table 7 below. 30 to 33 show SEM pictures of the PVC foams prepared in Examples 25 to 28.

Experiment
Raw material Example 25 Example 26 Example 27 Example 28 PVC 100.0 100.0 100.0 100.0 MDI 70.0 70.0 70.0 70.0 MA 3.0 4.0 5.0 6.0 AIBN 1.0 1.0 1.0 1.0 AC # 7000 6.0 6.0 6.0 6.0 DOP 28.0 28.0 28.0 28.0 Styrene 4.0 4.0 4.0 4.0 BR-105 2.0 2.0 2.0 2.0 n-Pentane 4.0 4.0 4.0 4.0 TM-700R 2.0 2.0 2.0 2.0 B8462 0.06 0.06 0.06 0.06 PPG 1000 11.0 11.0 11.0 11.0 Pigment 1.3 1.3 1.3 1.3

Example  29 to 33

A foam was prepared in the same manner as in Example 1 except that the molecular weight of polypropylene glycol was used and the amount of AC # 7000 was changed as shown in Table 8 below. 34 to 38 show SEM pictures of the PVC foams prepared in Examples 29 to 33.

Experiment
Raw material Example 29 Example 30 Example 31 Example 32 Example 33 PVC 100.0 100.0 100.0 100.0 100.0 MDI 70.0 70.0 70.0 70.0 70.0 PA 6.0 6.0 6.0 6.0 6.0 AIBN 1.0 1.0 1.0 1.0 1.0 AC # 7000 4.0 5.0 6.0 7.0 8.0 DOP 28.0 28.0 28.0 28.0 28.0 Styrene 4.0 4.0 4.0 4.0 4.0 BR-105 2.0 2.0 2.0 2.0 2.0 n-Pentane 4.0 4.0 4.0 4.0 4.0 TM-700R 2.0 2.0 2.0 2.0 2.0 PPG 1000 11.0 11.0 11.0 11.0 11.0 B8462 0.06 0.06 0.06 0.06 0.06 Pigment 1.3 1.3 1.3 1.3 1.3

Example  34 to 37

A foam was prepared in the same manner as in Example 1 except that the polypropylene glycol had a molecular weight of 1,000 and the amount of n-pentane added was changed as shown in Table 9 below. 39 to 42 show SEM pictures of the PVC foams prepared in Examples 34 to 37.

Experiment
Raw material Example 34 Example 35 Example 36 Example 37 PVC 100.0 100.0 100.0 100.0 MDI 70.0 70.0 70.0 70.0 PA 6.0 6.0 6.0 6.0 AIBN 1.0 1.0 1.0 1.0 AC # 7000 6.0 6.0 6.0 6.0 DOP 28.0 28.0 28.0 28.0 Styrene 4.0 4.0 4.0 4.0 BR-105 2.0 2.0 2.0 2.0 n-Pentane 2.0 3.0 4.0 5.0 TM-700R 2.0 2.0 2.0 2.0 B8462 0.06 0.06 0.06 0.06 PPG 1000 11.0 11.0 11.0 11.0 Pigment 1.3 1.3 1.3 1.3

Example  38 to 41

A foam was prepared in the same manner as in Example 1 except that the polypropylene glycol had a molecular weight of 1,000 and the amount of pyromellitic dianhydride was changed as shown in Table 10 below.

Experiment
Raw material Example 38 Example 39 Example 40 Example 41 PVC 100.0 100.0 100.0 100.0 MDI 70.0 70.0 70.0 70.0 PMDA 3.0 4.0 5.0 6.0 AIBN 1.0 1.0 1.0 1.0 AC # 7000 6.0 6.0 6.0 6.0 DOP 28.0 28.0 28.0 28.0 Styrene 4.0 4.0 4.0 4.0 BR-105 2.0 2.0 2.0 2.0 n-Pentane 4.0 4.0 4.0 4.0 TM-700R 2.0 2.0 2.0 2.0 B8462 0.06 0.06 0.06 0.06 PPG 1000 11.0 11.0 11.0 11.0 Pigment 1.3 1.3 1.3 1.3

Example  42 to 45

A foam was prepared in the same manner as in Example 1 except that polypropylene glycol had a molecular weight of 4,000 and the amount of phthalic anhydride added was changed as shown in Table 11 below. 43 to 46 show SEM pictures of the PVC foams prepared in these Examples 42 to 45.

Experiment
Raw material Example 42 Example 43 Example 44 Example 45 PVC 100.0 100.0 100.0 100.0 MDI 70.0 70.0 70.0 70.0 PA 3.0 4.0 5.0 6.0 AIBN 1.0 1.0 1.0 1.0 AC # 7000 6.0 6.0 6.0 6.0 DOP 28.0 28.0 28.0 28.0 Styrene 4.0 4.0 4.0 4.0 BR-105 2.0 2.0 2.0 2.0 n-Pentane 4.0 4.0 4.0 4.0 TM-700R 2.0 2.0 2.0 2.0 B8462 0.06 0.06 0.06 0.06 PPG 4000 11.0 11.0 11.0 11.0 Pigment 1.3 1.3 1.3 1.3

Example  46 to 49

A foam was prepared in the same manner as in Example 1 except that the molecular weight of polypropylene glycol was used and the amount of maleic anhydride added was changed as shown in Table 12 below. 47 to 50 show SEM pictures of the PVC foams prepared in Examples 46 to 49.

Experiment
Raw material Example 46 Example 47 Example 48 Example 49 PVC 100.0 100.0 100.0 100.0 MDI 70.0 70.0 70.0 70.0 MA 3.0 4.0 5.0 6.0 AIBN 1.0 1.0 1.0 1.0 AC # 7000 6.0 6.0 6.0 6.0 DOP 28.0 28.0 28.0 28.0 Styrene 4.0 4.0 4.0 4.0 BR-105 2.0 2.0 2.0 2.0 n-Pentane 4.0 4.0 4.0 4.0 TM-700R 2.0 2.0 2.0 2.0 B8462 0.06 0.06 0.06 0.06 PPG 4000 11.0 11.0 11.0 11.0 Pigment 1.3 1.3 1.3 1.3

Example  50 to 54

A foam was prepared in the same manner as in Example 1, except that the polypropylene glycol had a molecular weight of 4,000 and the amount of AC # 7000 was changed as shown in Table 13 below. 51 to 55 show SEM pictures of the PVC foams prepared in these Examples 50 to 54.

Experiment
Raw material Example 50 Example 51 Example 52 Example 53 Example 54 PVC 100.0 100.0 100.0 100.0 100.0 MDI 70.0 70.0 70.0 70.0 70.0 PA 6.0 6.0 6.0 6.0 6.0 AIBN 1.0 1.0 1.0 1.0 1.0 AC # 7000 4.0 5.0 6.0 7.0 8.0 DOP 28.0 28.0 28.0 28.0 28.0 Styrene 4.0 4.0 4.0 4.0 4.0 BR-105 2.0 2.0 2.0 2.0 2.0 n-Pentane 4.0 4.0 4.0 4.0 4.0 TM-700R 2.0 2.0 2.0 2.0 2.0 PPG 4000 11.0 11.0 11.0 11.0 11.0 B8462 0.06 0.06 0.06 0.06 0.06 Pigment 1.3 1.3 1.3 1.3 1.3

Example  55 to 58

A foam was prepared in the same manner as in Example 1 except that the molecular weight of polypropylene glycol was used and the amount of n-pentane was changed as shown in Table 14 below. 56 to 59 show SEM pictures of the PVC foams prepared in these Examples 55 to 58.

Experiment
Raw material Example 55 Example 56 Example 57 Example 58 PVC 100.0 100.0 100.0 100.0 MDI 70.0 70.0 70.0 70.0 MA 6.0 6.0 6.0 6.0 AIBN 1.0 1.0 1.0 1.0 AC # 7000 6.0 6.0 6.0 6.0 DOP 28.0 28.0 28.0 28.0 Styrene 4.0 4.0 4.0 4.0 BR-105 2.0 2.0 2.0 2.0 n-Pentane 2.0 3.0 4.0 5.0 TM-700R 2.0 2.0 2.0 2.0 B8462 0.06 0.06 0.06 0.06 PPG 4000 11.0 11.0 11.0 11.0 Pigment 1.3 1.3 1.3 1.3

Example  59 to 62

A foam was prepared in the same manner as in Example 1 except that the polypropylene glycol had a molecular weight of 4,000 and the amount of pyromellitic dianhydride was changed as shown in Table 15 below. 60 to 63 show SEM pictures of the PVC foams prepared in Examples 59 to 62.

Experiment
Raw material Example 59 Example 60 Example 61 Example 62 PVC 100.0 100.0 100.0 100.0 MDI 70.0 70.0 70.0 70.0 PMDA 3.0 4.0 5.0 6.0 AIBN 1.0 1.0 1.0 1.0 AC # 7000 6.0 6.0 6.0 6.0 DOP 28.0 28.0 28.0 28.0 Styrene 4.0 4.0 4.0 4.0 BR-105 2.0 2.0 2.0 2.0 n-Pentane 4.0 4.0 4.0 4.0 TM-700R 2.0 2.0 2.0 2.0 B8462 0.06 0.06 0.06 0.06 PPG 4000 11.0 11.0 11.0 11.0 Pigment 1.3 1.3 1.3 1.3

Test Example  1: structural analysis

As a result of analyzing the specimen prepared by cutting a part of the PVC foam prepared in the present invention by FT-IR spectroscopy, it can be seen that it has a structure of amide of PVC and polyurethane. The results are shown in FIG.

As shown in FIG. 2, the peak of C-Cl, which is a typical functional group of PVC, can be observed at 700-600cm ^-1 , and the NH peak of polyurea, which is another functional group, can be observed at 3400cm ^-1 . was, 1600cm ^-1 was observed in the group of C = O and the 3100 ~ 3000cm ^-1 were observed aromatic CH peaks.

Table 16 below shows the structure determination by infrared spectroscopy of the product specified as the reference substance.

Polymer Assigned structure Wave number (cm ^-1 ) Reported value Experimental value (a) PVC (1) CH ₂ , -CH 2900 2920 (2) CH ₂ 1430 1430 (3) CH-Cl 1250, 1330 1248 (4) C-Cl 700-600 700-600 (b) polyurea (5) NH 3500-3100 3500-3400 (6) CH 2950 2950 (7) C = O 1630, 1600 1600 (8) C-N 1250 1248 (9)- 719 719 (10)- 650-600 650-600 (c) polyimide (11) C = CH (aromatic) 3100-3000 3100-3000 (12) C = O 1780, 1715 1780, 1716 (13) C-N 1380 1378

Test Example  2

The density, tensile strength and compressive strength of the foam of the present invention was measured and shown in Tables 17 to 31 below.

Example 1 Example 2 Example 3 Example 4 density 0.52 0.60 0.64 0.68 The tensile strength 43 46 41 41 Compressive strength 153.27 139.29 142 141.53

Example 5 Example 6 Example 7 Example 8 density 0.57 0.57 0.51 0.60 The tensile strength 867 81 94 114 Compressive strength 172.65 162.65 149.5 158.9

Example 9 Example 10 Example 11 Example 12 density 0.66 0.55 0.66 0.85 The tensile strength 63 59 44 47 Shaft strength 246.12 186.84 195.4 168.3

Example 13 Example 14 Example 15 Example 16 density 0.61 0.51 0.81 0.70 The tensile strength 114 72 86 52 Compressive strength 214.08 183.57 196 212.14

Example 17 Example 18 Example 19 Example 20 density 0.58 0.59 0.60 0.77 The tensile strength 123 73 39 33 Compressive strength 261.73 198.55 197.16 215.10

Example 21 Example 22 Example 23 Example 24 density 0.53 0.55 0.64 0.77 The tensile strength 126 178 70 106 Compressive strength 232.86 224.18 206.02 244.80

Example 25 Example 26 Example 27 Example 28 density 0.57 0.57 0.60 0.55 The tensile strength 113 120 114 100 Compressive strength 232.76 231.33 192.04 189.49

Example 29 Example 30 Example 31 Example 32 Example 33 density 0.54 0.52 0.65 0.56 0.57 The tensile strength 81 88 75 95 120 Compressive strength 189.59 210.7 244.80 220.31 228.37

Example 34 Example 35 Example 36 Example 37 density 0.42 0.31 0.42 0.64 The tensile strength 56 77 89 95 Compressive strength 225.6 218.9 244.80 229.18

Example 38 Example 39 Example 40 Example 41 density 0.34 0.45 0.39 0.49 The tensile strength 70 123 66 76 Compressive strength 216 298 180.5 220.00

Example 42 Example 43 Example 44 Example 45 density 0.63 0.72 0.77 0.67 The tensile strength 128 101 160 119 Compressive strength 272.24 198.8 298.9 222.55

Example 46 Example 47 Example 48 Example 49 density 0.45 0.58 0.55 0.58 The tensile strength 171 168 141 193 Compressive strength 312.6 267.5 268.67 252.35

Example 50 Example 51 Example 52 Example 53 Example 54 density 0..63 0.55 0.51 0.78 0.56 The tensile strength 98 166 154 162 82 Compressive strength 258.27 260.61 222.55 274.90 205.51

Example 55 Example 56 Example 57 Example 58 density 0.45 0.63 0.43 0.33 The tensile strength 182 199 99 72 Compressive strength 298.6 303.06 222.55 266.43

Example 59 Example 60 Example 61 Example 62 density 0.67 0.60 0.59 0.46 The tensile strength 120 150 179 50 Compressive strength 294.8 247.8 264.0 251.4

As shown in the table, the mechanical properties vary depending on the density and the molecular weight of polypropylene glycol, so the result of measuring the physical properties is not significantly affected by the molecular weight of the polypropylene glycol, but tensile strength or compressive strength Mechanical properties, such as was shown to be greatly affected by the molecular weight of polypropylene glycol.

In general, the higher the molecular weight of polypropylene glycol is, the higher the mechanical properties and the better the magnetic digestibility. When maleic anhydride, phthalic anhydride, and pyromellitic anhydride, which are used as electron acceptors, were used to compare their properties, maleic anhydride generally showed better mechanical properties. It has been found that pentane shows a better tendency to foam. And for foaming PVC was used AC # 7000 foaming agent.

Test Example 3

The thermal conductivity of the foam of the present invention was measured and shown in Table 32 below.

Measures Δt _a Δt _b
Calculated Value time Temperature control cooling water Δt _R k ' _a K ' _b k test
start Temperature
(℃) Flow rate
l / h Inlet temperature
(℃) Outlet temperature
(℃) 1.61 3.38 test
finish t _o W t _in t _out A PA3 50 20 45 9 0.5 0.13 0.12 0.12 B MA4 0.5 0.13 0.12 0.12 C PA8 0.33 0.08 0.08 0.08 D MA8 0.5 0.13 0.12 0.12 Mean 0.45 0.12 0.11 0.11

A, B: foam using polypropylene glycol having a molecular weight of 400

C, D; Foam with Polypropylene Glycol of Molecular Weight 4,000

As shown in the table, the thermal conductivity of the foams of the phthalic anhydride and maleic anhydride was measured, it can be seen that the physical properties of the thermal conductivity is not high, it is also very stable thermally.

PVC rigid foam according to the present invention is a kind of multi-functional structural insulation material that the conventional general-purpose foam can alleviate the unavoidable use restrictions due to the lack of performance of insulation, heat resistance, cryogenic resistance, chemical resistance, self-extinguishing and mechanical strength The back light is particularly good, which makes it useful for a wide range of insulating building materials, refrigeration equipment and interior linings of aircraft vehicles, and interior cores of various composite materials. In particular, in the cryogenic insulation up to -195 ℃, it is much superior to any organic insulating material, and the performance is excellent when used for the insulation of liquefied natural gas, liquefied petroleum gas storage tanks and pipelines. Therefore, the PVC foam of the present invention is expected to be very useful for high functionalization and diversification of the insulation system.

Claims (8)

Method for producing a polyvinyl chloride (PVC) rigid foam, characterized in that it comprises the following steps:
(1) 3 to 8 parts by weight of organic acid anhydride, 1 part by weight of reaction initiator, 4 to 8 parts by weight of blowing agent AC # 7000, 28 parts by weight of plasticizer dioctylphthalate, 4 parts by weight of vinyl monomer, 2 parts by weight of BR-105, 2 2-5 parts by weight of the primary blowing agent n-pentane, 2 parts by weight of TM-700R, 0.06 parts by weight of B8462, 11 parts by weight of polypropylene glycol and 1.3 parts by weight of a pigment were mixed to prepare a premix resin, followed by polyvinyl chloride (PVC ) 100 parts by weight of the mixture, and then 70 parts by weight of isocyanate and mixing for 1 minute;
(2) foaming the mixture obtained in the above step at 180 ° C. on a press and then curing for 8 minutes; And
(3) curing the cured product obtained in the above step in water of 70 to 80 ° C. and then drying for 24 hours. The method of claim 1,
The production method characterized in that the PVC resin is PE-1311 resin. The method of claim 1,
Wherein said reaction initiator is azoisobutylonitrile. The method of claim 1,
The said isocyanate is toluene diisocyanate, methylene diphenyl diisocyanate, polymethylene diphenyl diisocyanate, The manufacturing method characterized by the above-mentioned. The method of claim 1,
Wherein said organic acid anhydride is maleic anhydride, phthalic anhydride or pyromellitic anhydride. The method of claim 1,
The vinyl monomer is styrene, acrylonitrile, methyl methacrylate or vinyl acetate, vinylpyridine production method characterized in that. The method of claim 1,
Wherein said polypropylene glycol is polypropylene glycol 400, polypropylene glycol 1000 or polypropylene glycol 4000. Polyvinylchloride rigid foam prepared according to the method according to any one of claims 1 to 7.

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